Shinobu Koda

A standard method to calibrate sonochemical efficiency of an individual reaction system.

Fricke reaction, KI oxidation and decomposition of porphyrin derivatives by use of seven types of sonochemical apparatus in four different laboratories were examined in the range of frequency of 19.5 kHz to 1.2 MHz. The ultrasonic energy dissipated into an apparatus was determined also by calorimetry. Sonochemical efficiency of Fricke reaction and KI oxidation was defined as the number of reacted molecule per unit ultrasonic energy. The sonochemical efficiency is independent of experimental conditions such as the shape of sample cell and irradiation instruments, but depends on the ultrasonic frequency. We propose the KI oxidation dosimetry using 0.1 moldm(-3) KI solution as a standard method to calibrate the sonochemical efficiency of an individual reaction system.

Ultrasonic degradation of water-soluble polymers

The ultrasonic degradation of the water-soluble polymers pullulan, poly(ethylene oxide) and polyvinylpyrrolidone was studied at a frequency of 500 kHz. The apparent degradation rate constants are 0.030 for pullulan, 0.076 for poly(ethylene oxide) and 0.032 min−1 for polyvinylpyrrolidone. The degradation mechanism was analysed by using Glynns model. The water-soluble polymers used here are degraded with a Gaussian probability by ultrasonic irradiation.

Inactivation of Escherichia coli and Streptococcus mutans by ultrasound at 500 kHz

This paper shows a systematic study of the 500 kHz frequency ultrasound efficiency on the microbial inactivation as a function of ultrasonic power delivered into the bacterial suspension. The inactivation of Escherichia coli IAM 12058, a Gram-negative bacterium and Streptococcus mutans JCM 5175, a Gram-positive bacterium is enhanced by increasing the ultrasonic power in the range of 1.7-12.4W and the logarithm of survival ratio decreases linearly with irradiation time, except for E. coli sonicated with the highest power level. The rate constants were estimated in the linear region of the plots representing survival ratio logarithm vs. sonication time. A better understanding of the inactivation process at 500kHz could be gained by suppressing the chemical effects with a radical scavenger. We find out that the rate constants increase with the ultrasonic power delivered into the solution and dramatically decrease by the addition of t-butanol as a radical scavenger to the bacterial suspension. For comparison, experiments were carried out at a low frequency level of 20kHz. It was found out that for the same ultrasonic power delivered into the bacterial suspension, the inactivation was slightly enhanced at 500kHz frequency. The examinations of bacterium performed with a TEM revealed lethal damages arising from the interaction of bacterial cells with the cavitational bubbles. A significant amount of empty cell envelopes as well as their cytoplasmatic content was detected. Thus, based on these new data, the mechanism of bacterial inactivation by ultrasounds at high frequency is discussed here.

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.

Effects of frequency and power of ultrasound on the size reduction of liposome

The solutions of liposome made of l-alpha-dilauroyl phosphatidylcholine are sonicated at various powers and frequencies (43-480kHz), and the resultant change in the size of liposome is measured by the dynamic light scattering method. The ultrasonic power dissipated into the solution is determined by the calorimetric method in order to compare the effects of ultrasound of different frequencies. The faster reduction of the mean size of liposome is achieved at the lower frequency. Comparing at the same frequency and total energy, short-time irradiation of strong ultrasound is more efficient than long-time irradiation of weak ultrasound. These results indicate that the small number of cavitation events with stronger physical disturbance on liposome can reduce the size of the liposome more efficiently than the large number of cavitation events with weaker disturbance.

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.

Effect of ultrasonic frequency on polymerization of styrene under sonication

The effect of ultrasonic frequency on polymerization of styrene under sonication at 50 degrees C was studied at the frequencies of 23.4, 45.7, 92, 518 kHz and 1 MHz. Polymerization under sonication was carried out at the ultrasonic intensity that gives the same reaction rate of decomposition of porphyrin. The magnitude of the polymerization rate increases in the order of 92, 45.7 and 23.4 kHz. At the high frequencies of 518 kHz and 1 MHz, no polymerization was observed. These facts mean that there is an optimum frequency in the range from 92 to 518 kHz for effective polymerization. The average-number molecular weights at the sonication time of 3 h are 5.5 x 10(4), 8.0 x 10(4) and 11.5 x 10(4) for the irradiated frequencies of 92, 45.7 and 23.4 kHz, respectively. Sonication for 3 h at 92 kHz gives polystyrene with very high polydispersity, about 5.0, in comparison with the results obtained at 23.4 and 45.7 kHz. These observations indicate that polymerization under sonication is influenced by the irradiated frequency.

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.

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.

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.