ABSTRACT
The temperature dependence of the Soret coefficient S(T)(T) in electrostatically charged magnetic colloids is investigated. Two different ferrofluids, with different particles' mean dimensions, are studied. In both cases we obtain a thermophilic behavior of the Soret effect. The temperature dependence of the Soret coefficient is described assuming that the nanoparticles migrate along the ionic thermoelectric field created by the thermal gradient. A model based on the contributions from the thermoelectrophoresis and variation of the double-layer energy, without fitting parameters, is used to describe the experimental results of the colloid with the bigger particles. To do so, independent measurements of the ζ potential, mass diffusion coefficient, and Seebeck coefficient are performed. The agreement of the theory and the experimental results is rather good. In the case of the ferrofluid with smaller particles, it is not possible to get experimentally reliable values of the ζ potential and the model described is used to evaluate this parameter and its temperature dependence.
ABSTRACT
The Seebeck and Soret coefficients of ionically stabilized suspension of maghemite nanoparticles in dimethyl sulfoxide are experimentally studied as a function of nanoparticle volume fraction. In the presence of a temperature gradient, the charged colloidal nanoparticles experience both thermal drift due to their interactions with the solvent and electric forces proportional to the internal thermoelectric field. The resulting thermodiffusion of nanoparticles is observed through forced Rayleigh scattering measurements, while the thermoelectric field is accessed through voltage measurements in a thermocell. Both techniques provide independent estimates of nanoparticle's entropy of transfer as high as 82 meV K(-1). Such a property may be used to improve the thermoelectric coefficients in liquid thermocells.
ABSTRACT
Magnetic fluids based on manganese ferrite nanoparticles were studied from the structural point of view through small angle x-rays scattering (SAXS) and from the magnetic point of view through zero-field cooling and field cooling (ZFC-FC) and ac susceptibility measurements (MS). Three different colloids with particles mean diameters of 2.78,3.42, and 6.15 nm were investigated. The size distribution obtained from SAXS measurements follows a log-normal behavior. The ZFC-FC and MS results revealed the presence of an important magnetic interaction between the nanoparticles, characterized by a magnetic correlation distance Λ. The colloidal medium can be pictures as composed by magnetic cluster constituted by N interacting particles. These magnetic clusters are not characterized by a physical aggregation of particles. The energy barrier energy obtained is consistent with the existence of this magnetic clusters. Besides the magnetic interaction between particles, confinement effects must be included to account for the experimental values of the magnetic energy barrier encountered.
ABSTRACT
The Soret coefficient (ST) of positively charged magnetic colloids was measured as a function of the nanoparticles' diameter. The Z-scan technique and the generalization of the thermal lens model proved to be a reliable technique to measure ST. We show that ST is negative and increases with the particle's diameter, being best described by a functional dependence of the type STâd0. Potentiometric and conductometric experiments show that the particle's surface charge decreases as the temperature increases, changing the electrostatic interaction between the nanoparticles. The temperature gradient imposed in the ferrofluid by the Gaussian laser beam leads to the formation of the particle's concentration gradient. The origin of this phenomenon is discussed in terms of the decrease of the particle's surface charge in the hottest region of the sample and the thermoelectric field due to the inhomogeneous distribution of hydrogenous ions present in the colloidal suspension.
ABSTRACT
In this work we focus on the surface charging properties of core shell ferrite nanoparticles dispersed in water, namely magnetic nanocolloids. This structural charge results from the Brönsted acid-base behavior of the particles surface sites and is achieved through hydrolysis reactions. It can be modeled by considering identical charged sites behaving as weak diprotic acids. Then, electrochemical techniques could be implemented to study the acid-base equilibrium between the particle surface and the colloid bulk solution. Simultaneous potentio-conductimetric titrations are therefore performed to determine the thermodynamical constants of the p H-dependent reactions and to obtain the p H variations of the surface charge density. The results reveal that the saturation value of the structural charge strongly depends on the nanoparticle mean size. For large particles, the surface tends to be fully ionized whereas for smaller particles the saturated structural charge decreases drastically. This surface charge reduction is attributed to the existence in smaller particles of metallic surface sites, which cannot be accessible to the proton charge. The existence of such dead sites would be related to hydroxo-bonded sites with very low acidity combined with a quantum size effect, which would affect the charging/discharging process at the surface of the semiconductor ferrite quantum dot.
