Yuriy Chushkin

Atomic-Scale Relaxation Dynamics and Aging in a Metallic Glass Probed by X-Ray Photon Correlation Spectroscopy

We use x-ray photon correlation spectroscopy to investigate the structural relaxation process in a metallic glass on the atomic length scale. We report evidence for a dynamical crossover between the supercooled liquid phase and the metastable glassy state, suggesting different origins of the relaxation process across the transition. Furthermore, using different cooling rates, we observe a complex hierarchy of dynamic processes characterized by distinct aging regimes. Strong analogies with the aging dynamics of soft glassy materials, such as gels and concentrated colloidal suspensions, point at stress relaxation as a universal mechanism driving the relaxation dynamics of out-of-equilibrium systems.

Compressed correlation functions and fast aging dynamics in metallic glasses

We present x-ray photon correlation spectroscopy measurements of the atomic dynamics in a Zr(67)Ni(33) metallic glass, well below its glass transition temperature. We find that the decay of the density fluctuations can be well described by compressed, thus faster than exponential, correlation functions which can be modeled by the well-known Kohlrausch-Williams-Watts function with a shape exponent β larger than one. This parameter is furthermore found to be independent of both waiting time and wave-vector, leading to the possibility to rescale all the correlation functions to a single master curve. The dynamics in the glassy state is additionally characterized by different aging regimes which persist in the deep glassy state. These features seem to be universal in metallic glasses and suggest a nondiffusive nature of the dynamics. This universality is supported by the possibility of describing the fast increase of the structural relaxation time with waiting time using a unique model function, independently of the microscopic details of the system.

Measuring temporal speckle correlations at ultrafast x-ray sources

We present a new method to extract the intermediate scattering function from series of coherent diffraction patterns taken with 2D detectors. Our approach is based on analyzing speckle patterns in terms of photon statistics. We show that the information obtained is equivalent to the conventional technique of calculating the intensity autocorrelation function. Our approach represents a route for correlation spectroscopy on ultrafast timescales at X-ray free-electron laser sources.

Three-dimensional coherent X-ray diffractive imaging of whole frozen-hydrated cells

Since its first experimental demonstration in 1999, coherent diffractive imaging (CDI) has been applied to image a broad range of samples using advanced synchrotron radiation, X-ray free-electron lasers, high harmonic generation and electrons. Here, the first experimental demonstration of cryogenic CDI for quantitative three-dimensional imaging of whole frozen-hydrated cells is reported. As a proof of principle, the three-dimensional mass density of the sub-cellular organization of a Neospora caninum cell is determined based on its natural contrast.

Revealing the fast atomic motion of network glasses

Still very little is known on the relaxation dynamics of glasses at the microscopic level due to the lack of experiments and theories. It is commonly believed that glasses are in a dynamical arrested state, with relaxation times too large to be observed on human time scales. Here we provide the experimental evidence that glasses display fast atomic rearrangements within a few minutes, even in the deep glassy state. Following the evolution of the structural relaxation in a sodium silicate glass, we find that this fast dynamics is accompanied by the absence of any detectable aging, suggesting a decoupling of the relaxation time and the viscosity in the glass. The relaxation time is strongly affected by the network structure with a marked increase at the mesoscopic scale associated with the ion-conducting pathways. Our results modify the conception of the glassy state and asks for a new microscopic theory.

A novel event correlation scheme for X‐ray photon correlation spectroscopy

X-ray photon correlation spectroscopy (XPCS) was employed to measure the time-dependent intermediate scattering function in an organic molecular glass former. Slow translational dynamics were probed in the glassy state and the correlation functions were calculated from two-dimensional speckle patterns recorded by a CCD detector. The image frames were analysed using a droplet algorithm together with an event correlation scheme. This method provides results analogous to standard intensity correlation algorithms but is much faster, hence addressing the recurrent problem of insufficient computing power for online analysis in XPCS. The event correlator has a wide range of potential future applications at synchrotrons and free-electron laser sources.

Low-frequency elastic behavior of a supercooled liquid

By X-ray photon correlation spectroscopy we quantify the influence of elasticity and viscosity on the capillary wave (CW) surface dynamics of a supercooled liquid. To fit the data a novel model combining Maxwell-Debye and Voigt-Kelvin viscoelasticity is derived yielding a saturation of relaxation rates at high q as well as an offset in the CW dispersion relation. Diffuse X-ray scattering confirms the result and data taken on the surface of supercooled polypropylene glycol (PPG-4000) evidence a low-frequency elastic plateau of the storage modulus. A possible connection between the observed solid-like response and the supercooled state is discussed.

Concentration fluctuations in a binary glass former investigated by x-ray photon correlation spectroscopy

We investigate structure and dynamics of concentration fluctuations in the binary glass former methyl-tetrahydrofuran and oligomeric methyl metacrylate by photon correlation spectroscopy with partially coherent x-rays from a synchrotron source. Although the system is macroscopically well miscible and optically clear in the full temperature range, calorimetric and dielectric measurements reveal two distinct glass transition temperatures. The relaxation of long range concentration fluctuations turns out to be diffusive and exponential only well above the upper glass transition temperature. As the characteristic time tau(cf) for concentration fluctuations shows a much weaker temperature dependence than the alpha-relaxation both traces finally intersect upon lowering the temperature. Thus, close to T(g), the concentration fluctuations show pronounced features of out-of-equilibrium dynamics such as compressed relaxation functions and a crossover to a ballistic wave vector dependence of tau(cf), like previously observed in various soft matter systems. Moreover, the analysis of time-resolved correlation functions reveals that the relaxation of concentration fluctuations around T(g) involves pronounced dynamic heterogeneities.

2D dynamical arrest transition in a mixed nanoparticle-phospholipid layer studied in real and momentum spaces.

We investigate the interfacial dynamics of a 2D self-organized mixed layer made of silica nanoparticles interacting with phospholipid (DPPC) monolayers at the air/water interface. This system has biological relevance, allowing investigation of toxicological effects of nanoparticles on model membranes and lung surfactants. It might also provide bio-inspired technological solutions, exploiting the self-organization of DPPC to produce a non-trivial 2D structuration of nanoparticles. The characterization of interfacial dynamics yields information on the effects of NPs on the mechanical properties, important to improve performances of systems such as colloidosomes, foams, creams. For this, we combine micro-tracking in real-space with measurement in momentum-space via x-ray photon-correlation spectroscopy and Digital Fourier Microscopy. Using these complementary techniques, we extend the spatial range of investigation beyond the limits of each one. We find a dynamical transition from Brownian diffusion to an arrested state driven by compression, characterized by intermittent rearrangements, compatible with a repulsive glass phase. The rearrangement and relaxation of the monolayer structure results dramatically hindered by the presence of NPs, which is relevant to explain some the mechanical features observed for the dynamic surface pressure response of these systems and which can be relevant for the respiratory physiology and for future drug-delivery composite systems.

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).