RESUMO
In this report, we investigate dynamic light scattering (DLS) from both randomly diffusing silica particles and acousto-responsive microgels in aqueous dispersions under ultrasonic vibration. Employing high-frequency ultrasound (US) with low amplitude ensures that the polymers remain intact without damage. We derive theoretical expressions for the homodyne autocorrelation function, incorporating the US term alongside the diffusion term. Subsequently, we successfully combined US with a conventional DLS system to experimentally characterize compact silica particles and microgels under the influence of US. Our model allows us to extract essential parameters, including particle size, frequency, and amplitude of particle vibration, based on the correlation function of the scattered light intensity. The studies involving non-responsive silica particles demonstrate that the US does not disrupt size determination, establishing them as suitable reference systems. In addition, we could be able to experimentally resolve the µs-order motion of particles for the first time. Microgels subjected to the US show the same swelling/shrinking behavior as that induced by temperature but with significantly faster kinetics. The findings of this study have potential applications in various industrial and biomedical fields such as smart coatings and drug delivery that benefit from the characterization of macromolecules subjected to the US. Furthermore, the current work may lead to characterizing the mechanical properties of soft particles based on their vibration amplitude extracted using this method.
RESUMO
Ultrasonic mixing is a well-established method to disperse and mix substances. However, the effects of ultrasound on dispersed soft particles as well as on their adsorption kinetics at interfaces remain unexplored. Ultrasound not only accelerates the movement of particles via acoustic streaming, but recent research indicates that it can also manipulate the interaction of soft particles with the surrounding liquid. In this study, it evaluates the adsorption kinetics of microgel at the water-oil interface under the influence of ultrasound. It quantifies how acoustic streaming accelerates the reduction of interfacial tension. It uses high-frequency and low-amplitude ultrasound, which has no destructive effects. Furthermore, it discusses the ultrasound-induced shrinking and thus interfacial rearrangement of the microgels, which plays a secondary but non-negligible role on interfacial tension reduction. It shows that the decrease in interfacial tension due to the acoustic streaming is stronger for microgels with higher cross-linker density. Moreover, it shows that ultrasound can induce a reversible decrease in interfacial tension due to the shrinkage of microgels at the interface. The presented results may lead to a better understanding in any field where ultrasonic waves meet soft particles, e.g., controlled destabilization in foams and emulsions or systems for drug release.
RESUMO
As a novel stimulus, we use high-frequency ultrasonic waves to provide the required energy for breaking hydrogen bonds between Poly(N-isopropylacrylamide) (PNIPAM) and water molecules while the solution temperature is maintained below the volume phase transition temperature (VPTT = 32 °C). Ultrasonic waves propagate through the solution and their energy will be absorbed due to the liquid viscosity. The absorbed energy partially leads to the generation of a streaming flow and the rest will be spent to break the hydrogen bonds. Therefore, the microgels collapse and become insoluble in water and agglomerate, resulting in solution turbidity. We use turbidity to quantify the ultrasound energy absorption and show that the acousto-response of PNIPAM microgels is a temporal phenomenon that depends on the duration of the actuation. Increasing the solution concentration leads to a faster turbidity evolution. Furthermore, an increase in ultrasound frequency leads to an increase in the breakage of more hydrogen bonds within a certain time and thus faster turbidity evolution. This is due to the increase in ultrasound energy absorption by liquids at higher frequencies.
RESUMO
Ultrasound propagation in liquids is highly influenced by its attenuation due to viscous damping. The dissipated energy will be partially absorbed by the liquid due to its dynamic viscosity as well as its bulk viscosity. The former results in the generation of a flow that is called acoustic streaming, and the latter is associated with the vibrational and rotational relaxation of liquid molecules. Measuring the ultrasonic wave attenuation due to the bulk viscosity is presented as a novel method in this article. Poly(N-isopropylacrylamide) (PNIPAM) microgels, which are soluble in several solvents such as water, were used as acousto-responsive markers in water, which upon absorption of ultrasonic energy undergo a volume phase transition due to the breakage of their hydrogen bonds. Thus, they become insoluble in water, and due to shrinking, their optical density increases. As a result, their agglomeration can be seen as a turbid medium. We managed to visualize the ultrasonic energy absorption due to the bulk viscosity using the turbidity since the excess acoustic energy on top of the absorbed energy for the translational motion of liquid is spent to break the hydrogen bonds between PNIPAM and water. In addition, to quantify the turbidity phenomenon, the total energy required for breaking hydrogen bonds in the solution is calculated, and its evolution, according to the input power intensity, is quantified by image processing. The effect of viscosity by changing the microgel concentration was investigated, and it is shown that an increasing microgel concentration increases the acoustic energy absorption rate much greater than its dynamic viscosity. Therefore, the bulk viscosity, as the responsible parameter for this increase, is measured directly from the energy of broken hydrogen bonds. The results show that at low solution concentration (0.2 wt %) the bulk viscosity is in the same order of magnitude as its dynamic viscosity. Increasing the concentrations to 1 and 5 wt % increases the bulk viscosity and consequently the structural relaxation time by 1 and 2 orders of magnitude, respectively.
RESUMO
A key step of inexpensive and scalable perovskite thin-film formation is defect-free fabrication through low-cost and facile post-treatment processes. Methods using high annealing temperatures are not favorable for the scale-up of solution-processed thin-film solar cells, particularly on plastic/flexible substrates. This contribution analyzes the effect of ultrasonic vibrations, a recently developed low-cost post-treatment process, on thin-film quality. Ultrasonic vibrations were applied to as-spun CH3NH3PbI3 perovskite thin films prepared with various solvents and antisolvents deposited on substrates with compact and mesoporous textures. Then, mechanisms of solvent evaporation, nucleation, and crystallization of perovskite grains were characterized during ultrasonic vibration. These studies demonstrate that ultrasonic vibration at low temperature facilitates heterogeneous crystallization of perovskite grains with a higher conversion of nuclei into crystal, compared with the conventional annealing process. Topographic scanning electron microscopy images confirm the dense and fully covered thin films after the evaporation of solvent. Furthermore, it is shown that crystal orientation does not change with the choice of solvent, eliminating the effect of solvent on the deposition of thin-film perovskites with this method. Therefore, this ultrasonic vibration post-treatment method is applicable to any solution-processed material and deposition technique, and it can be used to fabricate a range of thin-film devices and printed electronics.
RESUMO
In this paper, we experimentally studied the response frequency of oscillations of a sessile water droplet, subjected to horizontal vibrations at varying excitation frequency (5-250 Hz and 40 kHz) and amplitude (0.015 mm to 0.5 mm for low frequencies and 600nm for ultrasonic frequency), as well as static contact angle of the glass substrate ([Formula: see text], [Formula: see text] , [Formula: see text], [Formula: see text]). The droplets were pinned during the experiments and non-axisymmetric oscillation modes were excited due to the horizontal vibrations. For the first time, we observed that at a sufficiently high vibration amplitude, when the excitation frequency is lower than the smallest natural frequency of the sessile droplet, the droplet oscillates at a response frequency multiple of the excitation frequency. At higher excitation frequencies up to several hundreds of Hz, the droplet oscillates nearly at the excitation frequency. At ultrasonic excitation frequency, however, the droplet cannot follow the excitations, since there is a physical limitation for forming infinite modes (infinite wavenumber) on the surface of a small droplet. We have modeled these behaviors with a nonlinear mass-spring-damper system by combining two established models: the Duffing and Van der Pol equations, in order to simulate both nonlinear damping and stiffness.
RESUMO
Drying and crystallization of a thin liquid film of an ionic or a similar solution can cause dewetting in the resulting thin solid film. This paper aims at investigating this type of dewetting, herein termed "crystallization dewetting", using PbI2 dissolved in organic solvents as the model solution. PbI2 solid films are usually used in X-ray detection and lead halide perovskite solar cells. In this work, PbI2 films are fabricated using spin coating and the effect of major parameters influencing the crystallization dewetting, including the type of the solvent, solution concentration, drying temperature, spin speed, as well as imposed vibration on the substrate are studied on dewetting, surface profile and coverage, using confocal scanning laser microscopy. Simplified hydrodynamic governing equations of crystallization in thin films are presented and using a mathematical representation of the process, it is phenomenologically demonstrated that crystallization dewetting occurs due to the absorption and consumption of the solution surrounding a growing crystal. Among the results, it is found that a low spin speed (high thickness), a high solution concentration and a low drying temperature promote crystal growth, and therefore crystallization dewetting. It is also shown that imposed vibration on the substrate can affect the crystal size and crystallization dewetting.
