M. Pochylski

Communication: An extended model of liquid bridging

Recent phenomenological studies have drawn attention to an appealing effect, observed for the first time in 1893, today known as water-bridge. The phenomenon has been ascribed to unknown properties of water. We report some experimental results showing that, contrary to a widely common belief, the phenomenon is not to be related with water neither with a property of hydrogen bonded networks. Using a very simple model, we show that the liquid bridge phenomenon is originated by electrostatic effects and can be reproduced in any dense fluid with no respect of its peculiar molecular properties. This basic approach is able to reproduce many of the experimentally observed features of the bridge formation. In perspective of future investigations, the possible phenomena responsible of the bridge stability, after its formation, are briefly discussed.

Excess compressibility in binary liquid mixtures

Brillouin scattering experiments have been carried out on some mixtures of molecular liquids. From the measurement of the hypersonic velocities we have evaluated the adiabatic compressibility as a function of the volume fraction. We show how the quadratic form of the excess compressibility dependence on the solute volume fraction can be derived by simple statistical effects and does not imply any interaction among the components of the system other than excluded volume effects. This idea is supported by the comparison of the experimental results with a well-established prototype model, consisting of a binary mixture of hard spheres with a nonadditive interaction potential. This naive model turns out to be able to produce a very wide spectrum of structural and thermodynamic features depending on values of its parameters. An attempt has made to understand what kind of structural information can be gained through the analysis of the volume fraction dependence of the compressibility.

Emerging dynamics in surfactant-based liquid mixtures: Octanoic acid/bis(2-ethylhexyl) amine systems

This work focuses on the dynamic phenomena emerging in self-assembled transient intermolecular networks formed when two different surfactants are mixed. In particular, the relaxation processes in liquid mixtures composed by bis(2-ethylhexyl)amine (BEEA) and octanoic acid (OA) in the whole composition range has been investigated by dielectric spectroscopy and Brillouin spectroscopy. A thorough analysis of all the experimental data consistently suggests that, mainly driven by acid-base interactions arising when the two surfactants are mixed, supra-molecular aggregates formation causes the slowing down of molecular dynamics. This, in turn, reflects to longer-range relaxations. These changes have been found to be composition-dependent, involving strong departures of the mixture physico-chemical properties from an ideal behaviour, and reflecting the structural and dynamical features of local structures. In particular, the peculiar dynamic processes occurring in these local inter-molecular structures, have been found to be the factors responsible for the observed and quite surprising increase of direct-current conductivity which occurs when two different (and pretty non-conductive) surfactants are mixed. The discovery can be used not only to design novel materials for application purposes but also to shed more light on the basic principles regulating charge migration in structured liquid systems.

Brillouin scattering study of polyethylene glycol/water system below crystallization temperature.

We present the results of a Brillouin scattering experiment on aqueous mixtures of polyethylene glycol polymer cooled below their crystallization temperature. The shape of the registered spectrum changed considerably when the phase transition occurs. The Brillouin profile consisted of two peaks which has been interpreted as a result of the scattering of light on the local regions exhibiting different compressibility. Examination of the temperature dependence of the two Brillouin peak positions allows the identification of the specific microstructures present in the studied system. The existence of a complexlike hydration structure, stable against dilution and temperature agitation, was suggested. The nature and the behavior of the hydration complex is discussed in view of the earlier investigations in similar systems.

Some Evidence of Scaling Behavior in the Relaxation Dynamics of Aqueous Polymer Solutions

The structural relaxation behavior of aqueous solution of poly(ethylene glycol) and methoxy-capped poly(ethylene glycol), both of mean molecular mass 400 g/mol, is investigated by Brillouin scattering experiments. In both cases non-Debye relaxation processes have been detected, proceeding on the picosecond time scale. The average values of the detected relaxation time distributions fail to follow the simple Arrhenius behavior. The temperature evolution of the relaxation time is adequately fitted using the phenomenological Vogel-Fulcher-Tamman (VFT) model. In spite of the different temperature and concentration dependences observed for the two kinds of systems, with the exception of the highest samples concentrations, a unique scaling behavior has been found for the real and imaginary parts of the loss modulus plotted as a function of the reduced inverse temperature, T(0)/T, T(0) being the VFT arrest temperature. The presence of a unique scaling law in aqueous solutions of polymers characterized by different end groups suggests the establishment of similar hydrogen-bonded local structures. Within this scenario, water acts as a stabilizer and plays the main role bridging neighboring polymer chains. The possible physical interpretation of the obtained fit parameters is discussed, and the results are compared with other literature findings.

Nano-demixing as a novel strategy for magnetic field responsive systems: the case of dibutyl phosphate/bis(2-ethylhexyl)amine systems

Pure surfactant liquids and their binary mixtures, owing to the amphiphilic nature of the molecules involved, can exhibit nano-segregation and peculiar transport properties. The possibility of opportunely choosing the amphiphiles should lead to the formation of anisotropic aggregates that can be oriented by an external factor like a magnetic field. In this case some properties, like optical birefringence, can be induced by the use of a magnetic field. Dynamic features of dibutyl phosphate (DBP)/bis(2-ethylhexyl)amine (BEEA) mixtures have been investigated by FT-IR, NMR, rheometry, Brillouin scattering, and magnetically-induced birefringence measurements as a function of the BEEA mole fraction (X). It turns out that BEEA/DBP liquid mixtures, driven by H-bond formation, show zero-threshold percolating self-assembly with a maximum in viscosity and a minimum in molecular diffusion at 1 : 1 composition. Interestingly, it has been highlighted that nano-segregation takes place at X ≅ 0.7 with the formation of DBP-rich closed local structures that are fully-responsive to an external magnetic field, rendering the system birefringent. It is worth noting that this is the first observation of amphiphile-based micelles in amphiphilic medium. The analysis of all the experimental data consistently pointed out the microscopic factors involved in this peculiar phenomenon and in particular emphasized the role of specific polar and apolar interactions along with to steric effects in regulating the molecular organization in surfactant mixtures. This report presents novel clear, stable and anhydrous systems, fully responsive to a magnetic field with tunable optical birefringence, and opens new trends in the directed design of water-free optically-active fluids.

Volume crossover in deeply supercooled water adiabatically freezing under isobaric conditions

The irreversible return of a supercooled liquid to stable thermodynamic equilibrium often begins as a fast process which adiabatically drives the system to solid-liquid coexistence. Only at a later stage will solidification proceed with the expected exchange of thermal energy with the external bath. In this paper we discuss some aspects of the adiabatic freezing of metastable water at constant pressure. In particular, we investigated the thermal behavior of the isobaric gap between the molar volume of supercooled water and that of the warmer ice-water mixture which eventually forms at equilibrium. The available experimental data at ambient pressure, extrapolated into the metastable region within the scheme provided by the reference IAPWS-95 formulation, show that water ordinarily expands upon (partially) freezing under isenthalpic conditions. However, the same scheme also suggests that, for increasing undercoolings, the volume gap is gradually reduced and eventually vanishes at a temperature close to the currently estimated homogeneous ice nucleation temperature. This behavior is contrasted with that of substances which do not display a volumetric anomaly. The effect of increasing pressures on the alleged volume crossover from an expanded to a contracted ice-water mixture is also discussed.

Temperature dependent FCS studies using a long working distance objective: Viscosities of supercooled liquids and particle size

In this work, we describe new experimental setups for Fluorescence Correlation Spectroscopy (FCS) where a long working distance objective is used. Using these setups, FCS measurements in a broad temperature range for a small sample volume of about 50 μl can be performed. The use of specially designed cells and a dry long working distance objective was essential for avoiding temperature gradients in the sample. The performance of the new setups and a traditional FCS setup with immersion objectives is compared. The FCS data in combination with the Stokes-Einstein (SE) relation were used to obtain the values of the nanoviscosity of a fluid. We show for selected molecular van der Waals supercooled liquids that despite the fact that in these systems, a characteristic length scale can be defined, the nanoviscosity obtained from FCS is in a very good agreement with the macroscopic (rheometric) viscosity of the sample in a broad temperature range. This result corroborates the applicability of the SE relation to supercooled liquids at temperatures above 1.2 Tg. We also show that the temperature dependent size of thermoresponsive microgel particles can be determined by FCS using the designed cells and a long working distance objective in a broader size range without a need to use the correction procedure since the size correction is proportional to the square of the ratio of the hydrodynamic radius to the confocal volume size.

Simple way to analyze Brillouin spectra from turbid liquids

The shape of the Brillouin light-scattering spectrum recorded from turbid liquids is distinctly distorted compared to that from a transparent sample. The reason for this is the multiple scattering of light within the medium. The usual expression for the Brillouin spectrum does not apply to the multiple scattering situation. In this Letter, we consider a Brillouin spectrum from opaque samples composed of a distribution of spectra resulting from elementary scattering events, each occurring in single scattering vector conditions. We introduce a one-parameter test function to define the probability distribution of scattering events occurring at a given value of the scattering vector. The proposed procedure was tested on model liquids that consisted of suspensions of sub-micrometer spherical particles of different size and concentration, dispersed in different carrier liquids and studied as a function of temperature. Our analysis made it possible to account for the effect of multiple scattering and to recover the values of mechanical parameters describing the pure solvents.

Is electrospray emission really due to columbic forces

Electrospray ionization (ESI) is a widely adopted soft ionization method for mass spectroscopy (MS). In spite of the undeniable success of the technique, its mechanisms are difficult to be analytically modelled because the process is characterized by non-equilibrium conditions. The common belief is that the formation of gas-phase ions takes place at the apex of the Taylor cone via electrophoretic charging. The charge balance implies that a conversion of electrons to ions should occur at the metal-liquid interface of the injector needle. We have detected that the above description is based on unproved assumptions which are not consistent with the correct evaluation of the problem. The comparison between experiments performed under the usual geometry and observations obtained under symmetric field configurations suggests that the emitted droplets cannot be significantly charged or, at least, that any possible ionization mechanism is so poorly efficient to ensure that columbic forces cannot play a major role in jet formation, even in cases where the liquid consists of a solution of ionic species. Further work is required to clearly understand how ionization occurs in ESI-MS.