Mechanism of Particle Formation in Silver/Epoxy Nanocomposites Obtained through a Visible-Light-Assisted in Situ Synthesis.

A detailed understanding of the processes taking place during the in situ synthesis of metal/polymer nanocomposites is crucial to manipulate the shape and size of nanoparticles (NPs) with a high level of control. In this paper, we report an in-depth time-resolved analysis of the particle formation process in silver/epoxy nanocomposites obtained through a visible-light-assisted in situ synthesis. The selected epoxy monomer was based on diglycidyl ether of bisphenol A, which undergoes relatively slow cationic ring-opening polymerization. This feature allowed us to access a full description of the formation process of silver NPs before this was arrested by the curing of the epoxy matrix. In situ time-resolved small-angle X-ray scattering investigation was carried out to follow the evolution of the number and size of the silver NPs as a function of irradiation time, whereas rheological experiments combined with near-infrared and ultraviolet-visible spectroscopies were performed to interpret how changes in the rheological properties of the matrix affect the nucleation and growth of particles. The analysis of the obtained results allowed us to propose consistent mechanisms for the formation of metal/polymer nanocomposites obtained by light-assisted one-pot synthesis. Finally, the effect of a thermal postcuring treatment of the epoxy matrix on the particle size in the nanocomposite was investigated.

Layered material characterization using ultrasonic transmission. An inverse estimation methodology.

This paper presents an inverse methodology with the aim to characterize a layered material through the identification of acoustical and mechanical properties of its layers. The framework to accomplish this objective is provided by the Inverse Problems (IPs) theory. Material characterization refers to the detection and localization of discontinuities, as well as to the identification of physical properties, in order to predict the material behaviour. In this particular case, the IP is solved in the form of a parameter estimation problem, in which the goal is the estimation of the characteristic acoustic impedance, transit time, and attenuation of each layer. These parameters are directly related to relevant material properties, such as the speed of sound, density, elastic modulus and elastic energy dissipation constants. The IP solution is obtained by minimizing a cost functional formulated as the least squares error between the waveform calculated using an equivalent model, and the measured waveform obtained from ultrasonic transmission tests. The applied methodology allowed the accurate estimation of the desired parameters in materials composed of up to three layers. As a second contribution, a power law frequency dependence of the wave attenuation was identified for several homogeneous materials, based on the same ultrasonic transmission experiments.

Depth-profiling by confocal Raman microscopy (CRM): data correction by numerical techniques.

The data obtained in confocal Raman microscopy (CRM) depth profiling experiments with dry optics are subjected to significant distortions, including an artificial compression of the depth scale, due to the combined influence of diffraction, refraction, and instrumental effects that operate on the measurement. This work explores the use of (1) regularized deconvolution and (2) the application of simple rescaling of the depth scale as methodologies to obtain an improved, more precise, confocal response. The deconvolution scheme is based on a simple predictive model for depth resolution and the use of regularization techniques to minimize the dramatic oscillations in the recovered response typical of problem inversion. That scheme is first evaluated using computer simulations on situations that reproduce smooth and sharp sample transitions between two materials and finally it is applied to correct genuine experimental data, obtained in this case from a sharp transition (planar interface) between two polymeric materials. It is shown that the methodology recovers very well most of the lost profile features in all the analyzed situations. The use of simple rescaling appears to be only useful for correcting smooth transitions, particularly those extended over distances larger than those spanned by the operative depth resolution, which limits the strategy to the study of profiles near the sample surface. However, through computer simulations, it is shown that the use of water immersion objectives may help to reduce optical distortions and to expand the application window of this simple methodology, which could be useful, for instance, to safely monitor Fickean sorption/desorption of penetrants in polymer films/coatings in a nearly noninvasive way.

Scattering of intersecting spherical particles in the Rayleigh-Gans approximation.

In this work a novel semianalytical procedure to calculate the exact scattering behavior of complex particles made of intersecting spheres in the Rayleigh-Gans approximation is presented. Pickering emulsions, Janus particles, and lock and key particle colloids are particular cases of particles built from intersecting spheres. The proposed methodology is based on the decomposition of the complex particle as a sum of simpler components whose scattering properties can be evaluated using a simple integral. The procedure is developed for any number of spheres that intersect in pairs but it can be directly extended to intersections that involve more than two spheres at the same time. Some examples are presented to illustrate the application of the model to: (i) the study of the sensitivity of scattering spectra to detect complex particles from approximated model particles; (ii) the detection of different degrees of penetration of one particle into the other; (iii) the identification of the location of the cavity in particles that intersect with a spherical surface of contact; and (iv) the follow up of the evolution of a complex particle from a mix of its components.