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This review is dedicated to the topic of longitudinal rheology, a branch of rheology that is complementary to traditional shear rheology, and yet not as widely explored. Longitudinal rheology differs from typical shear rheology by the type of stress applied. Longitudinal stress is a wave, which causes liquid expansion and compression that occurs when ultrasound propagates through such liquid. The penetration depth of a longitudinal stress is much longer than for a shear stress, which allows this method to be used for studying liquid bulk properties at the MHz range. The concept of longitudinal rheology has been known for centuries, but only became available in commercial instruments as recently as the 1990s. We describe here the main principles of this technique, as well as present an overview of existing published applications, which include: —Bulk viscosity —Microviscosity —Hookean coefficient of inter-particle bonds —Newtonian liquid test at MHz range —Compressibility —Sol-gel transition —Micellar systems —Dissolution of polymers —Liquid mixtures

We have developed a novel microchannel geometry that allows us to perform simple DC electrophoresis to measure the electrophoretic mobility and zeta potential of analytes and particles. In standard capillary geometries, mobility measurements using DC fields are difficult to perform. Specifically, measurements in open capillaries require knowledge of the hard to measure and often dynamic wall surface potential. Although measurements in closed capillaries eliminate this requirement, the measurements must be performed at infinitesimally small regions of zero flow where the pressure driven-flow completely cancels the electroosmotic flow (Komagata Planes). Furthermore, applied DC fields lead to electrode polarization, further questioning the reliability and accuracy of the measurement. In contrast, our geometry expands and moves the Komagata planes to where velocity gradients are at a minimum, and thus knowledge of the precise location of a Komagata plane is not necessary. Additionally, our microfluidic device prevents electrode polarization because of fluid recirculation around the electrodes. We fabricated our device using standard MEMS fabrication techniques and performed electrophoretic mobility measurements on 500 nm fluorescently tagged polystyrene particles at various buffer concentrations. Results are comparable to two different commercial dynamic light scattering based particle sizing instruments. We conclude with guidelines to further develop this robust electrophoretic tool that allows for facile and efficient particle characterization.

This paper begins with a review of the studies dedicated to the electrochemistry of non-polar liquids performed during last century. There is a list of dozens of liquids that have been studied, as well as variety of electrolytes. There is an overview of 13 different experimental methods which have been employed for this task. The theoretical part of the review emphasizes the work done by Onsager, Debye, Fuoss, Kraus, Bjerrum and others in 1920s and 30s. They initiated and justified the fundamental ideas that serve as the scientific basis for modern handbooks on non-aqueous electrochemistry. Many of these papers from 1930s and later are reviewed here. The second part of this paper is dedicated to the electrochemistry of non-polar liquids containing surfactants. These substances can serve as electrolytes if ionic. However, their main function is to enhance the solvation of ions, providing steric stabilization that minimizes ion re-association and ion-pair formation. Consequently, the classical “dissociation model” requires some modification when applied to surfactant solutions. There are also two additional theoretical models suggested specifically for surfactant solutions in non-polar liquids: the “disproportionation model” for dry inverse micelles, and the “fluctuation model” by Eicke, Borkovec, and Das-Gupta for microemulsions. Charged microemulsion droplets can serve as ions, which justifies the inclusion of this theory in this review. In addition, we can study (with a well defined theory) the transition from microemulsion droplet to dry inverse micelle ion by reducing water content. Studying this transition reveals some important features of both systems. We present here these three theories and apply them for interpreting experimental data (mostly conductivity) in four different systems, all of which are non-polar systems containing surfactants: solutions of ionic surfactants, solutions of non-ionic surfactants, microemulsions with ionic surfactants, and microemulsions with non-ionic surfactants.

It is known that nonpolar liquids can be ionized by adding surfactants, either ionic or nonionic. Surfactant molecules serve as solvating agents, building inverse micelles around ions, and preventing their association back into neutral molecules. According to the Bjerrum-Onsager-Fuoss theory, these inverse micelle ions should form "ion pairs." This, in turn, leads to nonlinear dependence of the conductivity on the concentration. Surprisingly, ionic surfactants exhibit linear conductivity dependence, which implies that these inverse micelle ions do not form ion pairs. Theory predicts the existence of two ionic strength ranges, which are separated by a certain critical ion concentration. Ionic strength above the critical one is proportional to the square root of the ion concentration, whereas it becomes linear below the critical concentration. Critical ion concentration lies within the range of 10(-11) -10(-7) mol/L when ion size ranges from 1 to 3 nm. Critical ion concentration is related, but not equal, to a certain surfactant concentration (critical concentration of ion-pairs formation (CIPC)) because only a fraction of the surfactant molecules is incorporated into the micelles ions. The linear conductivity dependence for ionic surfactants indicates that the corresponding CIPC is above the range of studied concentrations, perhaps, due to rather large ion size. The same linearity is a sign that charged inverse micelles structure and fraction are concentration independent due to strong charge-dipole interaction in the charge micelle core. This also proves that CIPC is independent of critical concentration of micelle formation. Nonionic surfactants, on the other hand, exhibit nonlinear conductivity dependence apparently due to smaller ion sizes.

Ultrasound attenuates when propagating through aqueous dispersions of carbon nanotubes. We established a significant difference in the ultrasound attenuation frequency spectra for the nanotubes oriented either along or across the ultrasound beam. This effect can be used for calculating geometrical and rheological properties of nanofiber materials dispersed in liquids. Keywords: Ultrasound attenuation, Carbon nanotubes, Nanofibers