Andrei Fluerasu

Glass–glass transition during aging of a colloidal clay

Colloidal suspensions are characterized by a variety of microscopic interactions, which generate unconventional phase diagrams encompassing fluid, gel and glassy states and offer the possibility to study new phase and/or state transitions. Among these, glass-glass transitions are rare to be found, especially at ambient conditions. Here, through a combination of dilution experiments, X-ray photon correlation spectroscopy, small angle X-ray scattering, rheological measurements and Monte Carlo simulations, we provide evidence of a spontaneous glass-glass transition in a colloidal clay. Two different glassy states are distinguished with evolving waiting time: a first one, dominated by long-range screened Coulombic repulsion (Wigner glass) and a second one, stabilized by orientational attractions (Disconnected House of Cards glass), occurring after a much longer time. These findings may have implications for heterogeneously charged systems out-of-equilibrium and for applications where a fine control of the local order and/or long term stability of the amorphous materials are required.

Microphase Structure of Poly(N-isopropylacrylamide) Hydrogels As Seen by Small- and Wide-Angle X-ray Scattering and Pulsed Field Gradient NMR

Above the lower critical solution temperature T(c) (ca. 34 degrees C), poly(N-isopropylacrylamide) hydrogels become weakly hydrophobic and undergo microphase separation. Macroscopic deswelling, however, is extraordinarily slow, the out-of equilibrium state of the gel being conserved for many days. In this article the structure of the microphase-separated state above T(c) is probed by small-angle X-ray scattering and by pulsed field gradient NMR of the protons of water, both in the water phase and in the polymer-rich phase. Above T(c) the gel comprises two microphases, separated by smooth interfaces. The cavities occupied by the water phase form a connected network. The diffusion rate of the water molecules in this phase varies from one cavity to another and can be described by a Gaussian distribution. Water molecules belonging to the polymer-rich phase are also mobile, but their self-diffusion coefficient D is greatly diminished. Absence of compartmentalization of the water phase implies that the slow deswelling rate of the gel is not due to trapping of the water phase.

Dynamics and rheology under continuous shear flow studied by x-ray photon correlation spectroscopy

X-ray photon correlation spectroscopy (XPCS) has emerged as a unique technique allowing the measurement of dynamics of materials on mesoscopic lengthscales. One of the most common problems associated with the use of bright x-ray beams is beam-induced radiation damage, and this is likely to become an even more limiting factor at future synchrotron and free-electron laser sources. Flowing the sample during data acquisition is one of the simplest methods allowing the radiation damage to be limited. In addition to distributing the dose over many different scatterers, the method also enables new functionalities such as time-resolved studies. Here, we further develop a recently proposed experimental technique that combines XPCS and continuously flowing samples. More specifically, we use a model colloidal suspension to show how the macroscopic advective response to flow and the microscopic dissipative dynamics (diffusion) can be quantified from the x-ray data. Our results show very good quantitative agreement with a Poisseuille-flow hydrodynamical model combined with Brownian mechanics. The method has many potential applications, e.g. in the study of dynamics of glasses and gels under continuous shear/flow, protein aggregation processes and the interplay between dynamics and rheology in complex fluids.

Slow dynamics in an azopolymer molecular layer studied by x-ray photon correlation spectroscopy.

We report the results of x-ray photon correlation spectroscopy (XPCS) experiments on multilayers of a photosensitive azo-polymer which can be softened by photoisomerization. Time correlation functions have been measured at different temperatures and momentum transfers (q) and under different illumination conditions (dark, UV or visible). The correlation functions are well described by the Kohlrausch-Williams-Watts (KWW) form with relaxation times that are proportional to q(-1). The characteristic relaxation times follow the same Vogel-Fulcher-Tammann law describing the bulk viscosity of this polymer. The out-of-equilibrium relaxation dynamics following a UV photoperturbation are accelerated, which is in agreement with a fluidification effect previously measured by rheology. The transient dynamics are characterized by two times correlation function, and dynamical heterogeneity is evidenced by calculating the variance χ of the degree of correlation as a function of ageing time. A clear peak in χ appears at a well defined time τ(C) which scales with q(-1) and with the ageing time, in a similar fashion as previously reported in colloidal suspensions [O. Dauchot, Phys. Rev. Lett. 95, 265701 (2005)]. From an accurate analysis of the correlation functions we could demonstrate a temperature and light dependent cross-over from compressed KWW to simple exponential behavior.

Deswelling kinetics of PNIPA gels

Faster-than-exponential decays and hyper-diffusive dispersion relationships detected in X-ray photon correlation spectroscopy measurements on poly(N-isopropyl acrylamide) hydrogels in the out-of-equilibrium jammed state are the result of uniform deswelling.

Dynamics in shear flow studied by X-ray Photon Correlation Spectroscopy

Abstract.X-ray Photon Correlation Spectroscopy was used to measure the diffusive dynamics of colloidal particles in a shear flow. The results presented here show how the intensity autocorrelation functions measure both the diffusive dynamics of the particles and their flow-induced, convective motion. However, in the limit of low flow/shear rates, it is possible to obtain the diffusive component of the dynamics, which makes the method suitable for the study of the dynamical properties of a large class of complex soft-matter and biological fluids. An important benefit of this experimental strategy over more traditional X-ray methods is the minimization of X-ray-induced beam damage. While the method can be applied also for photon correlation spectroscopy in the visible domain, our analysis shows that the experimental conditions under which it is possible to measure the diffusive dynamics are easier to achieve at higher q values (with X-rays).

Dynamics in dense hard-sphere colloidal suspensions

The dynamic behavior of a hard-sphere colloidal suspension was studied by x-ray photon correlation spectroscopy and small-angle x-ray scattering over a wide range of particle volume fractions. The short-time mobility of the particles was found to be smaller than that of free particles even at relatively low concentrations, showing the importance of indirect hydrodynamic interactions. Hydrodynamic functions were derived from the data, and for moderate particle volume fractions (Φ≤ 0.40) there is good agreement with earlier many-body theory calculations by Beenakker and Mazur [Physica A 120, 349 (1984)]. Important discrepancies appear at higher concentrations, above Φ≈ 0.40, where the hydrodynamic effects are overestimated by the Beenakker-Mazur theory, but predicted accurately by an accelerated Stokesian dynamics algorithm developed by Banchio and Brady [J. Chem. Phys. 118, 10323 (2003)]. For the relaxation rates, good agreement was also found between the experimental data and a scaling form predicted by the mode coupling theory. In the high concentration range, with the fluid suspensions approaching the glass transition, the long-time diffusion coefficient was compared with the short-time collective diffusion coefficient to verify a scaling relation previously proposed by Segrè and Pusey [Phys. Rev. Lett. 77, 771 (1996)]. We discuss our results in view of previous experimental attempts to validate this scaling law [L. Lurio et al., Phys. Rev. Lett. 84, 785 (2000)].

Photon statistics and speckle visibility spectroscopy with partially coherent X-rays.

A new approach is proposed for measuring structural dynamics in materials from multi-speckle scattering patterns obtained with partially coherent X-rays. Coherent X-ray scattering is already widely used at high-brightness synchrotron lightsources to measure dynamics using X-ray photon correlation spectroscopy, but in many situations this experimental approach based on recording long series of images (i.e. movies) is either not adequate or not practical. Following the development of visible-light speckle visibility spectroscopy, the dynamic information is obtained instead by analyzing the photon statistics and calculating the speckle contrast in single scattering patterns. This quantity, also referred to as the speckle visibility, is determined by the properties of the partially coherent beam and other experimental parameters, as well as the internal motions in the sample (dynamics). As a case study, Brownian dynamics in a low-density colloidal suspension is measured and an excellent agreement is found between correlation functions measured by X-ray photon correlation spectroscopy and the decay in speckle visibility with integration time obtained from the analysis presented here.

Structural Dynamics of Materials Probed by X-Ray Photon Correlation Spectroscopy

In this chapter we discuss coherent X-ray scattering, photon statistics of speckle patterns, and X-ray photon correlation spectroscopy (XPCS). XPCS is a coherent X-ray scattering technique used to characterize dynamic properties of condensed matter by recording a fluctuating speckle pattern. In the experiments, the time correlation function of the scattered intensity is calculated at different momentum transfers Q and thereby detailed information about the dynamics is obtained. Recently, XPCS applications have broadened to include the study of nonequilibrium and heterogeneous dynamics, e.g., in systems close to jamming or at the glass transition. This is enabled through multi-speckle techniques where a 2D area detector (CCDs or pixel detectors) is employed, and the correlation function is evaluated by averaging over subsets of equivalent pixels (same Q). In this manner time averaging can be avoided, and the time-dependent dynamics is quantified by the so-called two-times correlation functions. Higher-order correlation functions may also be calculated to investigate questions related to non-Gaussian dynamics and dynamical heterogeneity. We discuss recent forefront applications of XPCS in the study of soft and hard condensed matter dynamics, including phase-separation dynamics of colloid-polymer mixtures, motion of Au nanoparticles at the air-water interface, dynamics of atoms in metallic crystals and glasses, and domain coarsening in phase-ordering binary alloys.

Robust X-ray angular correlations for the study of meso-structures

As self-assembling nanomaterials become more sophisticated, it is becoming increasingly important to measure the structural order of finite-sized assemblies of nano-objects. These mesoscale clusters represent an acute challenge to conventional structural probes, owing to the range of implicated size scales (10 nm to several micrometres), the weak scattering signal and the dynamic nature of meso-clusters in native solution environments. The high X-ray flux and coherence of modern synchrotrons present an opportunity to extract structural information from these challenging systems, but conventional ensemble X-ray scattering averages out crucial information about local particle configurations. Conversely, a single meso-cluster scatters too weakly to recover the full diffraction pattern. Using X-ray angular cross-correlation analysis, it is possible to combine multiple noisy measurements to obtain robust structural information. This paper explores the key theoretical limits and experimental challenges that constrain the application of these methods to probing structural order in real nanomaterials. A metric is presented to quantify the signal-to-noise ratio of angular correlations, and it is used to identify several experimental artifacts that arise. In particular, it is found that background scattering, data masking and inter-cluster interference profoundly affect the quality of correlation analyses. A robust workflow is demonstrated for mitigating these effects and extracting reliable angular correlations from realistic experimental data.