Degradation of cellulose in NaOH and NaOH/urea aqueous solutions by ultrasonic irradiation.

Ultrasonic degradation of cellulose with low molecular weight in NaOH and NaOH/urea solutions was investigated at 20 and 500 kHz frequencies by measuring the solution viscosity. The viscosity decreased with sonication time. A small difference in viscosity ratio which is defined as the ratio of specific viscosity of solution after and before sonication was observed for the longer sonication. The degrees of the polymerization were reduced from 230 to 150 for 30 min sonication at 20 kHz and for 120 min sonication at 500 kHz. From XRD measurement, it was estimated that the crystallinity after sonication was the same as that before sonication. The crystallinity structure after sonication corresponded to Cellulose II. The yield of water-soluble components after ultrasonic irradiation was 20 wt% at 20 kHz in NaOH solutions and 30 wt% for 720 min at 500 kHz in NaOH/urea solution. Oligosaccharides and their derivative were detected by the SEC analysis of water-soluble components after sonication.

Dependence of cavitation, chemical effect, and mechanical effect thresholds on ultrasonic frequency.

Cavitation, chemical effect, and mechanical effect thresholds were investigated in wide frequency ranges from 22 to 4880kHz. Each threshold was measured in terms of sound pressure at fundamental frequency. Broadband noise emitted from acoustic cavitation bubbles was detected by a hydrophone to determine the cavitation threshold. Potassium iodide oxidation caused by acoustic cavitation was used to quantify the chemical effect threshold. The ultrasonic erosion of aluminum foil was conducted to estimate the mechanical effect threshold. The cavitation, chemical effect, and mechanical effect thresholds increased with increasing frequency. The chemical effect threshold was close to the cavitation threshold for all frequencies. At low frequency below 98kHz, the mechanical effect threshold was nearly equal to the cavitation threshold. However, the mechanical effect threshold was greatly higher than the cavitation threshold at high frequency. In addition, the thresholds of the second harmonic and the first ultraharmonic signals were measured to detect bubble occurrence. The threshold of the second harmonic approximated to the cavitation threshold below 1000kHz. On the other hand, the threshold of the first ultraharmonic was higher than the cavitation threshold below 98kHz and near to the cavitation threshold at high frequency.

Study on the temperature-dependent coupling among viscosity, conductivity and structural relaxation of ionic liquids.

The frequency-dependent viscosity and conductivity of three imidazolium-based ionic liquids were measured at several temperatures in the MHz region, and the results are compared with the intermediate scattering functions determined by neutron spin echo spectroscopy. The relaxations of both the conductivity and the viscosity agree with that of the intermediate scattering function at the ionic correlation when the relaxation time is short. As the relaxation time increases, the relaxations of the two transport properties deviate to lower frequencies than that of the ionic structure. The deviation begins at a shorter relaxation time for viscosity than for conductivity, which explains the fractional Walden rule between the zero-frequency values of the shear viscosity and the molar conductivity.

Dielectric and shear relaxations of ionic liquid composed of symmetric ions.

The frequency-dependent conductivity and shear viscosity of an ionic liquid composed of symmetric ions were determined experimentally in the MHz region. The ionic liquid studied was tetraoctylphosphonium bromide. An isomer with an asymmetric cation, trihexyltetradecylphosphonium bromide, was also investigated to clarify the possible role of the reorientational motion of the cations in the two relaxation spectra. Both the conductivity and the shear viscosity show relaxation in the MHz region, and these relaxation spectra scarcely depend on the asymmetry of the cations. It is, therefore, concluded that the coupling of the reorientational mode of cations with these relaxation spectra is marginal, and that these spectra reflect mainly the frequency-dependent translational motion of ions.

Quantitative analysis of conductivity and viscosity of ionic liquids in terms of their relaxation times.

The frequency-dependent viscosity and conductivity of various ionic liquids were measured experimentally, and their mean relaxation times were determined. The relaxation times of the viscosity and conductivity were approximately correlated with their respective zero-frequency limiting values. The Walden products, however, appeared to have no correlation with the ratio of the relaxation time of viscosity to that of conductivity in general. When the alkyl chain of the cation is as short as butyl, more viscous ionic liquids tend to show larger difference between two relaxation times and larger Walden products. Lengthening the alkyl chain of the cation decreases the Walden product while slightly increasing the relaxation time ratio, which was elucidated in terms of the decrease in the high-frequency shear modulus. In addition, the contribution of the mesoscopic structure to viscosity was suggested in the case of the ionic liquid with the longest alkyl chain studied in this work, 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide.

Separation characteristics of alcohol from aqueous solution by ultrasonic atomization.

The generation rate of ultrasonically atomized droplets and the alcohol concentration in droplets were estimated by measuring the flow rate and the alcohol concentration of vapors from a bulk solution with a fountain. The effect of the alcohol concentration in the bulk solution on the generation rate of droplets and the alcohol concentration in droplets were investigated. The ultrasonic frequency was 2.4MHz, and ethanol and methanol aqueous solutions were used as samples. The generation rate of droplets for ethanol was smaller than that for methanol at the same alcohol molar fraction in the bulk solution. For both solutions, at low alcohol concentration in the bulk solution, the alcohol concentration in droplets was lower than that in vapors and the atomized droplets were visible. On the other side, at high concentration, the concentration in droplets exceeded that in vapors and the atomized droplets became invisible. These results could be explained that the alcohol-rich clusters in the bulk solution were preferentially atomized by ultrasonic irradiation. The concentration in droplets for ethanol was higher than that for methanol at low alcohol concentration because the amount of alcohol-rich clusters was larger. When the alcohol molar fraction was greater than 0.6, the atomized droplets almost consisted of pure alcohol.

Quantification of frequency dependence of mechanical effects induced by ultrasound.

The physical or mechanical effects induced by ultrasound were investigated through the viscosity change in degradation of polymers. The viscosity change was observed with polyethylene oxide in both aqueous and benzene solution; while polystyrene in only benzene solution. The frequency of ultrasound in these experiments varies from 20 kHz to 1 MHz, under a constant dissipated power. The viscosity ratio and the apparent degradation rate were obtained as a function of the irradiation frequency. From the analysis of these experiments, the mechanical effects are found to slow down above 100 kHz when the frequency increases. In case of the analysis of solution viscosity, since this method yields the same apparent results in both aqueous and benzene solutions, our study propose an alternative simple, cost effective method to quantify the mechanical effects in sonochemistry.

Bimodal dielectric relaxation of electrolyte solutions in weakly polar solvents.

The dielectric relaxation spectra of dilute electrolyte solutions in solvents of small dielectric constants are investigated both theoretically and experimentally. The theoretical calculation in our previous work [T. Yamaguchi, T. Matsuoka, and S. Koda, J. Chem. Phys. 135, 164511 (2011)] is reanalyzed, and it is shown that the dielectric relaxation spectra are composed of three components, namely, the relaxation of ionic atmosphere, the reorientational relaxation of ion pairs, and the collision between ions. The relaxation frequency of the slowest one increases with increasing the concentration, and the slower two relaxations, those of ionic atmosphere and ion pairs, merge into one at the concentration where the Debye length is comparable to the size of ions. Experimentally, the dielectric relaxation spectra of some electrolytes in two solvents, tetrahydrofuran and tetraglyme, are determined at frequencies from 300 kHz to 200 MHz, and the presence of the slower two relaxations was confirmed. The concentration dependence of the relaxation frequency is also in harmony with the theoretical calculation. The relationship between the dielectric relaxation spectra and the concentration dependence of the ionic conductivity is discussed.

Relationship between microviscosity and high-frequency viscosity of polymer gel electrolytes.

The frequency-dependent viscosity and conductivity of polymer gel electrolytes are investigated in the megahertz region to clarify how polymer affects the ionic mobility. The electric conductivity shows no dispersion below 10 MHz, where slow dynamics of polymer are observed in shear relaxation spectra, which indicates that the ionic motion is uncorrelated with the slow dynamics of polymers that determines the steady state shear viscosity. On the other hand, the shear viscosity around 100 MHz is somewhat correlated with the direct-current (DC) molar conductivity, suggesting that the measurement of the high-frequency viscosity can be a probe of the so-called microviscosity associated with the mobility of an ion.

Interpretation of the variation of the Walden product of ionic liquids with different alkyl chain lengths in terms of relaxation spectra.

The shear relaxation spectra and the alternating-current (AC) conductivity of 1-alkyl-3-methylimidazolium hexafluorophosphate were measured in the MHz region, with the chain lengths varied from butyl to octyl. The relaxation times of both the conductivity and shear viscosity increased with increasing chain length approximately in proportion to the variation of the reciprocal molar conductivity. On the other hand, the increase in the shear viscosity was smaller than that of the relaxation time, which indicates that the high-frequency shear modulus decreases with the chain length. The decrease in the the Walden product with the chain length is thus ascribed to that of the high-frequency shear modulus.

Rheological bases for empirical rules on shear viscosity of lubrication oils.

The shear relaxation spectra of various lubrication oils were measured at 5-205 MHz and 10-70 °C, and the variation of the steady-state shear viscosity (η0) was divided into the contributions of the high-frequency shear modulus (G∞) and relaxation time (τ). The temperature dependence of η0 was dominated by that of τ. The increase in molecular weight accompanies both increase in τ and decrease in G∞, and the increase in η0 results from the larger effect of the former. The flexibility of the chain reduced τ, while its effect on G∞ was rather small. The introduction of phenyl or cyclohexyl groups enhanced G∞. Oils of larger G∞ tend to exhibit a larger temperature dependence of η0.

Numerical simulation of liquid velocity distribution in a sonochemical reactor.

Ultrasonically induced flow is an important phenomenon observed in a sonochemical reactor. It controls the mass transport of sonochemical reaction and enhances the reaction performance. In the present paper, the liquid velocity distribution of ultrasonically induced flow in the sonochemical reactor with a transducer at frequency of 490 kHz has been numerically simulated. From the comparison of simulation results and experimental data, the ultrasonic absorption coefficient in the sonochemical reactor has been evaluated. To simulate the liquid velocity near the liquid surface above the transducer, which is the main sonochemical reaction area, it is necessary to include the acoustic fountain shape into the computational domain. The simulation results indicate that the liquid velocity increases with acoustic power. The variation of liquid height also influences the behavior of liquid velocity distribution and the mean velocity above the transducer centre becomes a maximum when the liquid height is 0.4m. The liquid velocity decreases with increasing the transducer plate radius at the same ultrasonic power.

Relationship between mesoscale dynamics and shear relaxation of ionic liquids with long alkyl chain.

The shear relaxation spectra of three imidazolium-based ionic liquids, 1-methyl-3-octylimidazolium chloride ([C(8)mim][Cl]), 1-methyl-3-octylimidazolium hexafluorophosphate ([C(8)mim][PF(6)]), and 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C(12)mim][TFSA]) were measured and compared with the intermediate scattering functions determined with neutron spin echo (NSE) spectroscopy. The shear relaxation is slower than that predicted from the relaxation of the main peak of the structure factor that is common to other molecular liquids, whereas it is faster than that from the relaxation of the pre-peak, that corresponds to the correlation length of about 10 nm specific to ionic liquids with an intermediately long alkyl chain. The role of the pre-peak structure in the mechanism of shear viscosity of ionic liquids is discussed based on the comparison between NSE and shear relaxations.

Effects of lithium salts on shear relaxation spectra of pyrrolidinium-based ionic liquids.

The shear relaxation spectra of the solutions of lithium salts in ionic liquids composed of N-methyl-N-propylpyrrolidinium cation paired with bis(trifluoromethanesulfonyl)amide (TFSA(-)) or bis(fluorosulfonyl)amide (FSA(-)) anions are determined from 5 to 205 MHz at various concentrations of lithium salts. The addition of lithium salt retards the shear relaxation, together with the increase in the shear viscosity. The normalized spectra reduce to a single curve when plotted against the product of the frequency and zero-frequency shear viscosity, which indicates that the increase in the shear viscosity by lithium salts is ascribed to the increase in the relaxation time. The difference in the shear viscosity of TFSA- and FSA-based ionic liquids is also elucidated in terms of the shear relaxation time. The relationship with previous studies on ionic mobility and liquid structure is also discussed.

Frequency-domain investigation of the ionic mobility of triflate salts in tetrahydrofuran.

The frequency-dependent molar conductivities of two triflate salts, tetrabutylammonium triflate (TBATf) and lithium triflate (LiTf), in tetrahydrofuran are measured in the microwave frequency domain at the concentrations where the direct-current molar conductivity increases with concentration. The relaxation frequency of the conductivity of TBATf increases with concentration as was demonstrated by a simulation and theoretical calculation on a simple model system. However, the low-frequency side of the relaxation of the conductivity of LiTf grows with increasing concentration, suggesting the presence of large aggregates such as triple ions. The molar conductivities of both salts at 20 GHz are about an order of magnitude smaller than those predicted by the Nernst-Einstein relationship, indicating the importance of the picosecond or faster dynamics in the determination of the absolute value of the conductivity.

Effects of frequency and a radical scavenger on ultrasonic degradation of water-soluble polymers.

Ultrasonic degradation of methyl cellulose, pullulan, dextran and poly(ethylene oxide) in aqueous solutions was investigated at the frequencies of 20 and 500 kHz, where the ultrasonic power delivered into solutions was kept constant (22 W). The number average molecular mass and the polydispersity were obtained as a function of sonication time. The degradation under sonication at the 500 kHz frequency proceeded faster in comparison with the 20 kHz sonication for four polymers. The addition of a radical scavenger, t-BuOH, resulted in suppression of degradation of water-soluble polymers. The degradation rate constants were estimated from the plot of molecular weight against sonication time. The degradation rate of methyl cellulose was the largest one among the investigated polymers. The difference in the degradation rates was discussed in terms of the flexibility and the hydrodynamic radius of polymer chains in aqueous solutions.

A calorimetric study of energy conversion efficiency of a sonochemical reactor at 500 kHz for organic solvents.

It would seem that the economic viability is yet to be established for a great number of sonochemical processes, owning to their perfectible ultrasonic equipments. Industrial scale sonoreactors may become more important as a result of mastering the parameters with influence on their energy balance. This work related the solvent type to the energy efficiency as the first step of a complex study aiming to assess the energy balance of sonochemical reactors at 500 kHz. Quantitative measurements of ultrasonic power for water and 10 pure organic solvents were performed by calorimetry for a cylindrically shaped sonochemical reactor with a bottom mounted vibrating plate. It was found that the ultrasonic power is strongly related to the solvent, the energy conversion for organic liquids is half from that of water and there is a drop in energy efficiency for filling levels up to 250 mm organic solvents. Surface tension, viscosity and vapor pressure influence the energy conversion for organic solvents, but it is difficult explain these findings based on physical properties of solvents alone. The apparent intensity of the atomization process shows a good agreement with the experimentally determined values for energy conversion for water and the solvent group studied here. This study revealed that to attain the same ultrasonic power level, more electrical energy is need for organic solvents as compared to water. The energy balance equation has been defined based on these findings by considering an energy term for atomization.

Shear relaxation of imidazolium-based room-temperature ionic liquids.

The frequency-dependent shear viscosities of four representative imidazolium-based room-temperature ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([bmim][TFSA]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF(6)]), and 1-methyl-3-octylimidazolium hexafluorophosphate ([omim][PF(6)]), are measured from 5 to 205 MHz with shear impedance spectroscopy. A relaxation is observed in the measured frequency range in all cases. This is the first report on the shear relaxation of ionic liquids at room temperature, to our best knowledge. Comparing the spectra of the common cations, [bmim][TFSA] and [bmim][PF(6)], the normalized relaxation spectra, eta(nu)/eta(0), reduce to a single curve when plotted against eta(0)nu, where nu and eta(0) stand for the frequency and shear viscosity, respectively. The lower viscosity of the TFSA salt is thus elucidated by the shorter relaxation time. The lower viscosity at higher temperature is also attributed to the shorter relaxation time. On the other hand, the increase in the length of the alkyl chain of the cation leads to the lower-frequency shift of the relaxation frequency on the eta(0)nu scale. Therefore, the higher viscosity of the omim salt is the result of the compensation of the longer relaxation time for the smaller high-frequency shear modulus. In addition, the relaxation time distribution becomes broader with increasing chain length, which can be ascribed to the heterogeneity of the liquid structure.

The effects of acoustic flow and mechanical flow on the sonochemical efficiency in a rectangular sonochemical reactor.

Visualization of cavitation behavior in a rectangular sonochemical reactor at 490 kHz was carried out by a laser sheet technique and the distribution of liquid flow was measured by a laser Doppler velocimeter. The pattern of liquid flow and distribution of acoustic pressure of the rectangular sonochemical reactor were investigated as a function of the input power from 10 to 50 W. The liquid moved upward above the transducer at every power. As increasing the input power, the random flow out side the cylindrical part above the transducer changed into the convective one and the region of the visualized standing wave which was formed in the cylindrical part changed with the input power. The position showing the sonochemical luminescence exists inside or near the region where the standing wave was visualized. Introduction of a stirrer resulted in disturbance of liquid flow and expanded the position showing the sonochemical luminescence, but the luminescence intensity was weakened. The sonochemical efficiency was enhanced by about twice by introduction of the stirrer. From these results, we discussed the effects of liquid flow on sonochemical efficiency with and without a stirrer.

Electric and mechanical relaxations of LiClO4-propylene carbonate systems in 100 MHz region.

The electric and mechanical relaxation spectra of the solutions of lithium perchlorate (LiClO(4)) in propylene carbonate (PC)-based mixed solvents are studied. The frequency-dependent dielectric susceptivity and electric conductivity from 0.05 to 20 GHz are determined with microwave reflectometry, and the shear relaxation from 15 to 95 MHz is measured with quartz-crystal shear impedance spectroscopy. An electric relaxation is observed at several hundreds of megahertz in a PC solution of LiClO(4) at a concentration higher than 0.5 mol dm(-3). The amplitude and frequency of the relaxation become larger and lower, respectively, with an increase in the concentration of salt. With the addition of such less-polar cosolvents as dimethyl carbonate, 1,4-dioxane or benzene at fixed concentrations (0.5, 2.0, and 3.0 mol dm(-3)) of the salt, decreases in the amplitude and relaxation time are observed. Shear relaxation is also observed at the corresponding frequency, and the dependence on the concentration of the salts and cosolvents is similar. The zero-frequency conductivity and shear viscosity are discussed in terms of the relaxation.