Insights into the precipitation kinetics of CaCO3 particles in the presence of polystyrene sulfonate using in situ small-angle X-ray scattering.

The formation of calcium carbonate (CaCO3) nanoparticles (NPs) in the presence of polystyrene sulfonate (PSS) as an additive was examined by time-resolved small-angle X-ray scattering (SAXS) in a flow system that mimics experimental conditions used at home facilities where the precipitation can be achieved in a beaker. The experiments were carried out at low concentrations to remain in the dilute regime. A model-independent analysis was performed using the Porod invariant which defines the scale factor, leaving only the distribution of radii as the adjustable parameter. The presence of the PSS additive strongly retards the precipitation of CaCO3 NPs. The formation of NPs reaches a state of equilibrium after a few minutes. Here, it is shown that the concentration of precursors at a fixed PSS concentration plays a key role in determining the size of the NPs obtained. A full analysis of the SAXS patterns was carried out using the Hurd-Flower model to account for the weaker intensity decay than the classical Porod behaviour. The temporal evolution of the particle radii was determined. Wide-angle X-ray scattering experiments carried out simultaneously show that the particles formed have the structure of vaterite with growth consistent with the evolution of the Porod invariant.

Experimental 3D coherent diffractive imaging from photon-sparse random projections.

The routine atomic resolution structure determination of single particles is expected to have profound implications for probing structure-function relationships in systems ranging from energy-storage materials to biological molecules. Extremely bright ultrashort-pulse X-ray sources - X-ray free-electron lasers (XFELs) - provide X-rays that can be used to probe ensembles of nearly identical nanoscale particles. When combined with coherent diffractive imaging, these objects can be imaged; however, as the resolution of the images approaches the atomic scale, the measured data are increasingly difficult to obtain and, during an X-ray pulse, the number of photons incident on the 2D detector is much smaller than the number of pixels. This latter concern, the signal 'sparsity', materially impedes the application of the method. An experimental analog using a conventional X-ray source is demonstrated and yields signal levels comparable with those expected from single biomolecules illuminated by focused XFEL pulses. The analog experiment provides an invaluable cross check on the fidelity of the reconstructed data that is not available during XFEL experiments. Using these experimental data, it is established that a sparsity of order 1.3 × 10-3 photons per pixel per frame can be overcome, lending vital insight to the solution of the atomic resolution XFEL single-particle imaging problem by experimentally demonstrating 3D coherent diffractive imaging from photon-sparse random projections.

X-ray nanotomography of coccolithophores reveals that coccolith mass and segment number correlate with grid size.

Coccolithophores of the Noëlaerhabdaceae family are covered by imbricated coccoliths, each composed of multiple calcite crystals radially distributed around the periphery of a grid. The factors that determine coccolith size remain obscure. Here, we used synchrotron-based three-dimensional Coherent X-ray Diffraction Imaging to study coccoliths of 7 species of Gephyrocapsa, Emiliania and Reticulofenestra with a resolution close to 30 nm. Segmentation of 45 coccoliths revealed remarkable size, mass and segment number variations, even within single coccospheres. In particular, we observed that coccolith mass correlates with grid perimeter which scales linearly with crystal number. Our results indirectly support the idea that coccolith mass is determined in the coccolith vesicle by the size of the organic base plate scale (OBPS) around which R-unit nucleation occurs every 110-120 nm. The curvation of coccoliths allows inference of a positive correlation between cell nucleus, OBPS and coccolith sizes.

Ultra-small-angle X-ray photon correlation spectroscopy using the Eiger detector.

Successful implementation of the single-photon-counting Eiger 500k pixel array detector for sub-millisecond X-ray photon correlation spectroscopy (XPCS) measurements in the ultra-small-angle scattering region is reported. The performance is demonstrated by measuring the dynamics of dilute silica colloids in aqueous solvents when the detector is operated at different counter depths, 4, 8 and 12 bit. In the fastest mode involving 4 bit parallel readout, a stable frame rate of 22 kHz is obtained that enabled measurement of intensity-intensity autocorrelation functions with good statistics down to the 50 µs range for a sample with sufficient scattering power. The high frame rate and spatial resolution together with large number of pixels of the detector facilitate the investigation of sub-millisecond dynamics over a broad length scale by multispeckle XPCS. This is illustrated by an example involving phoretic motion of colloids during the phase separation of the solvent.

Hard X-rays as pump and probe of atomic motion in oxide glasses.

Nowadays powerful X-ray sources like synchrotrons and free-electron lasers are considered as ultimate tools for probing microscopic properties in materials. However, the correct interpretation of such experiments requires a good understanding on how the beam affects the properties of the sample, knowledge that is currently lacking for intense X-rays. Here we use X-ray photon correlation spectroscopy to probe static and dynamic properties of oxide and metallic glasses. We find that although the structure does not depend on the flux, strong fluxes do induce a non-trivial microscopic motion in oxide glasses, whereas no such dependence is found for metallic glasses. These results show that high fluxes can alter dynamical properties in hard materials, an effect that needs to be considered in the analysis of X-ray data but which also gives novel possibilities to study materials properties since the beam can not only be used to probe the dynamics but also to pump it.

How many photons are needed to reconstruct random objects in coherent X-ray diffractive imaging?

This paper presents an investigation of the reconstructibility of coherent X-ray diffractive imaging diffraction patterns for a class of binary random `bitmap' objects. Combining analytical results and numerical simulations, the critical fluence per bitmap pixel is determined, for arbitrary contrast values (absorption level and phase shift), both for the optical near- and far-field. This work extends previous investigations based on information theory, enabling a comparison of the amount of information carried by single photons in different diffraction regimes. The experimental results show an order-of-magnitude agreement.

Strong infrared photoluminescence in highly porous layers of large faceted Si crystalline nanoparticles.

Almost all physical processes in solids are influenced by phonons, but their effect is frequently overlooked. In this paper, we investigate the photoluminescence of large silicon nanoparticles (approximately 100 nm size, synthesized by chemical vapor deposition) in the visible to the infrared detection range. We find that upon increasing laser irradiance, an enormous photoluminescence emission band appears in the infrared. Its intensity exhibits a superlinear power dependence, increasing over four orders of magnitude in the investigated pump power range. Particles of different sizes as well as different shapes in porous layers are investigated. The results are discussed taking into account the efficient generation of phonons under high-power pumping, and the reduced capability, porosity dependent, of the silicon nanoparticles to exchange energy with each other and with the substrate. Our findings are relevant for heat management strategies in silicon.

Resolution enhancement by extrapolation of coherent diffraction images: a quantitative study on the limits and a numerical study of nonbinary and phase objects.

In coherent diffractive imaging, the resolution of the reconstructed object is limited by the numerical aperture of the experimental setup. We present here a theoretical and numerical study for achieving super-resolution by postextrapolation of coherent diffraction images, such as diffraction patterns or holograms. We demonstrate that a diffraction pattern can unambiguously be extrapolated from only a fraction of the entire pattern and that the ratio of the extrapolated signal to the originally available signal is linearly proportional to the oversampling ratio. Although there could be in principle other methods to achieve extrapolation, we devote our discussion to employing iterative phase retrieval methods and demonstrate their limits. We present two numerical studies; namely, the extrapolation of diffraction patterns of nonbinary and that of phase objects together with a discussion of the optimal extrapolation procedure.

Field induced anisotropic cooperativity in a magnetic colloidal glass.

The translational dynamics of a repulsive colloidal glass-former is probed by time-resolved X-ray Photon Correlation Spectroscopy. In this dense dispersion of charge-stabilized and magnetic nanoparticles, the interaction potential can be tuned, from quasi-isotropic to anisotropic by applying an external magnetic field. This powerful control parameter finely tunes the anisotropy of the intricate energy landscape in the colloidal glass-former, which is seen here as a new tunable model-system to probe the dynamical heterogeneities at the approach of the glass transition. Both structural and dynamical anisotropies are reported on interparticle lengthscales associated with highly anisotropic cooperativity, almost two orders of magnitude larger in the field direction than in the perpendicular direction and in zero field.

Correlated heterogeneous dynamics in glass-forming polymers.

We report x-ray photon correlation spectroscopy experiments on the dynamics of the glass-former polypropylene glycol covering a temperature range from room temperature to the glass transition at T(g)=205 K using silica tracer particles. Three temperature regimes are identified: At high temperatures, Brownian motion of the tracer particles is observed. Near T(g), the dynamics is hyperdiffusive and ballistic. Around 1.12T(g), we observe an intermediate regime. Here the stretching exponent of the Kohlrausch-Williams-Watts function becomes q dependent. By analyzing higher-order correlations in the scattering data, we find that dynamical heterogeneities dramatically increase in this intermediate-temperature regime. This leads to two effects: increasing heterogeneous dynamics and correlated motion at temperatures close to and below 1.12T(g).

Controlling the dynamics of a bidimensional gel above and below its percolation transition.

The morphology and the microscopic internal dynamics of a bidimensional gel formed by spontaneous aggregation of gold nanoparticles confined at the water surface are investigated by a suite of techniques, including grazing-incidence x-ray photon correlation spectroscopy (GI-XPCS). The range of concentrations studied spans across the percolation transition for the formation of the gel. The dynamical features observed by GI-XPCS are interpreted in view of the results of microscopic imaging; an intrinsic link between the mechanical modulus and internal dynamics is demonstrated for all the concentrations. Our work presents an example of a transition from a stretched to a compressed correlation function actively controlled by quasistatically varying the relevant thermodynamic variable. Moreover, by applying a model proposed some time ago by Duri and Cipelletti [Europhys. Lett. 76, 972 (2006)] we are able to build a master curve for the shape parameter, whose scaling factor allows us to quantify a "long-time displacement length." This characteristic length is shown to converge, as the concentration is increased, to the "short-time localization length" determined by pseudo-Debye-Waller analysis of the initial contrast. Finally, the intrinsic dynamics of the system is then compared with that induced by means of a delicate mechanical perturbation applied to the interface.

Silica nanoparticles as tracers of the gelation dynamics of a natural biopolymer physical gel.

The gelation of methylcellulose in water has been studied by X-ray photon correlation spectroscopy, electrophoresis and rheological measurements by looking into the dynamics of silica nanoparticles as tracers in the polymer matrix. The temperature and scattering vector dependence of the structural relaxation time is investigated at the nanometric length scale during the formation of the strong gel state. We find a stress-dominated dynamics on approaching the gel state, characterized by a hyper-diffusive motion of the silica particles. These results support the idea of a unifying scenario for the dynamics of complex out of equilibrium soft materials.

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.

Three-dimensional coherent diffractive imaging on non-periodic specimens at the ESRF beamline ID10.

The progress of tomographic coherent diffractive imaging with hard X-rays at the ID10 beamline of the European Synchrotron Radiation Facility is presented. The performance of the instrument is demonstrated by imaging a cluster of Fe2P magnetic nanorods at 59 nm 3D resolution by phasing a diffraction volume measured at 8 keV photon energy. The result obtained shows progress in three-dimensional imaging of non-crystalline samples in air with hard X-rays.

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 ß 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.

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.

Dynamics at the liquid-vapor interface of a supercooled organic glass former.

We investigated the dynamics near the liquid-vapor interface of the supercooled model organic glass former dibutyl phthalate by using surface-sensitive x-ray scattering techniques. Our results reveal significant enhancement of the relaxation rate over a wide length-scales range. The analysis of the dispersion relation of long-wavelength surface fluctuations yields a nonzero value of the share modulus near the free surface. At the molecular level, the dynamics in the near surface region (10-15 nm) is inhomogeneous. The mobility is decreasing with increasing distance from the free surface. Below the bulk glass transition, two distinct relaxation times were observed differing by 1 order of magnitude. The observed fast relaxation proves the existence of a high mobility liquidlike surface layer of 10 nm thickness on top of a frozen in bulk system.

Two-dimensional heterogeneous dynamics at the surface of a colloidal suspension.

We report on an x-ray photon correlation spectroscopy experiment investigating the surface structure and dynamics of colloidal particles suspended in a supercooled viscous liquid. The static structure factor in the direction parallel and perpendicular to the surface reveals a more disordered structure at the surface as compared to the bulk. The particles display heterogeneous ballistic dynamics parallel to the surface. The particle dynamics in the direction perpendicular to the surface is much slower and does not show the hallmarks of ballistic motion.

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.

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

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).