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A combined X-ray photon correlation spectroscopy and rheology study is carried out to capture the evolution of structure, fast particle-scale dynamics, and moduli (elastic and loss) at early times of gel formation near the fluid–gel boundary of a suspension of nanoparticles. The system is comprised of moderately concentrated suspensions of octadecyl silica in decalin (ϕ = 0.2) undergoing thermoreversible gelation. Near the gel boundary, the rate of gel formation is very sensitive to changes in attraction strength. However, we find that at different attraction strengths, the system goes through identical intermediate states of microscopic and macroscopic behavior, even though the absolute time needed to form a gel varies by orders of magnitude. We identify a single dimensionless time parameter, tw/tg, where tw is the wait time following the quench and tg is the rheologically determined gel time, that captures the similarity in gel formation at a range of attraction strengths. Following a temperature quench below the gel boundary, the system is initially fluidlike and forms diffusive clusters (∼8.5 times the particle diameter). After a lag-time, tL, clusters aggregate to form a network like structure which is characterized by the onset of mechanical rigidity and a rapid growth in microscopic relaxation times. At tg, the Baxter parameter obtained from adhesive hard sphere fits of the structure factor attains a constant value corresponding to the theoretical percolation boundary, thus demonstrating that gelation is percolation driven. [ABSTRACT FROM AUTHOR]

pyXPCSviewer, a Python-based graphical user interface that is deployed at beamline 8-ID-I of the Advanced Photon Source for interactive visualization of XPCS results, is introduced. pyXPCSviewer parses rich X-ray photon correlation spectroscopy (XPCS) results into independent PyQt widgets that are both interactive and easy to maintain. pyXPCSviewer is open-source and is open to customization by the XPCS community for ingestion of diversified data structures and inclusion of novel XPCS techniques, both of which are growing demands particularly with the dawn of near-diffraction-limited synchrotron sources and their dedicated XPCS beamlines. [ABSTRACT FROM AUTHOR]

The performance of the new 52 kHz frame rate Rigaku XSPA‐500k detector was characterized on beamline 8‐ID‐I at the Advanced Photon Source at Argonne for X‐ray photon correlation spectroscopy (XPCS) applications. Due to the large data flow produced by this detector (0.2 PB of data per 24 h of continuous operation), a workflow system was deployed that uses the Advanced Photon Source data‐management (DM) system and high‐performance software to rapidly reduce area‐detector data to multi‐tau and two‐time correlation functions in near real time, providing human‐in‐the‐loop feedback to experimenters. The utility and performance of the workflow system are demonstrated via its application to a variety of small‐angle XPCS measurements acquired from different detectors in different XPCS measurement modalities. The XSPA‐500k detector, the software and the DM workflow system allow for the efficient acquisition and reduction of up to ∼109 area‐detector data frames per day, facilitating the application of XPCS to measuring samples with weak scattering and fast dynamics. [ABSTRACT FROM AUTHOR]

This paper illustrates the use of spatial filtering with a horizontal slit near the source to enlarge the horizontal coherence in an experimental station and produce a diffraction‐limited round focus at an insertion device beamline for X‐ray photon correlation spectroscopy experiments. Simple expressions are provided to guide the optical layout, and wave propagation simulations confirm their applicability. The two‐dimensional focusing performance of Be compound refractive lenses to produce a round diffraction‐limited focus at 11 keV capable of generating a high‐contrast speckle pattern of an aerogel sample is demonstrated. The coherent scattering patterns have comparable speckle sizes in both horizontal and vertical directions. The focal spot sizes are consistent with hybrid ray‐tracing calculations. Producing a two‐dimensional focus on the sample can be helpful to resolve speckle patterns with modern pixel array detectors with high visibility. This scheme has now been in use since 2019 for the 8‐ID beamline at the Advanced Photon Source, sharing the undulator beam with two separate beamlines, 8‐ID‐E and 8‐ID‐I at 7.35 keV, with increased partially coherent flux, reduced horizontal spot sizes on samples, and good speckle contrast. [ABSTRACT FROM AUTHOR]

Small‐angle X‐ray photon correlation spectroscopy (XPCS) measurements spanning delay times from 826 ns to 52.8 s were performed using a photon‐counting pixel array detector with a dynamic range of 0–3 (2 bits). Fine resolution and a wide dynamic range of time scales was achieved by combining two modes of operation of the detector: (i) continuous mode, where data acquisition and data readout are performed in parallel with a frame acquisition time of 19.36 µs, and (ii) burst mode, where 12 frames are acquired with frame integration times of either 2.56 µs frame−1 or 826 ns frame−1 followed by 3.49 ms or 1.16 ms, respectively, for readout. The applicability of the detector for performing multi‐speckle XPCS was demonstrated by measuring the Brownian dynamics of 10 nm‐radius gold and 57 nm‐radius silica colloids in water at room temperature. In addition, the capability of the detector to faithfully record one‐ and two‐photon counts was examined by comparing the statistical distribution of photon counts with expected probabilities from the negative binomial distribution. It was found that in burst mode the ratio of 2 s to 1 s is markedly smaller than predicted and that this is attributable to pixel‐response dead‐time. [ABSTRACT FROM AUTHOR]

Multi‐speckle X‐ray photon correlation spectroscopy (XPCS) is a powerful technique for characterizing the dynamic nature of complex materials over a range of time scales. XPCS has been successfully applied to study a wide range of systems. Recent developments in higher‐frame‐rate detectors, while aiding in the study of faster dynamical processes, creates large amounts of data that require parallel computational techniques to process in near real‐time. Here, an implementation of the multi‐tau and two‐time autocorrelation algorithms using the Hadoop MapReduce framework for distributed computing is presented. The system scales well with regard to the increase in the data size, and has been serving the users of beamline 8‐ID‐I at the Advanced Photon Source for near real‐time autocorrelations for the past five years. [ABSTRACT FROM AUTHOR]

ABSTRACT We present an X-ray photon correlation spectroscopy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of colloids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the saturation concentration of added polymer, in which small clusters of nanoparticles form via a short-range depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily governed by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 752-760 [ABSTRACT FROM AUTHOR]

The Vertically Integrated Photon Imaging Chip (VIPIC) was custom-designed for X-ray photon correlation spectroscopy, an application in which occupancy per pixel is low but high time resolution is needed. VIPIC operates in a sparsified streaming mode in which each detected photon is immediately read out as a time- and position-stamped event. This event stream can be fed directly to an autocorrelation engine or accumulated to form a conventional image. The detector only delivers non-zero data (sparsified readout), greatly reducing the communications overhead typical of conventional frame-oriented detectors such as charge-coupled devices or conventional hybrid pixel detectors. This feature allows continuous acquisition of data with timescales from microseconds to hours. In this work VIPIC has been used to measure X-ray photon correlation spectroscopy data on polystyrene latex nano-colliodal suspensions in glycerol and on colloidal suspensions of silica spheres in water. Relaxation times of the nano-colloids have been measured for different temperatures. These results demonstrate that VIPIC can operate continuously in the microsecond time frame, while at the same time probing longer timescales. [ABSTRACT FROM AUTHOR]

Using high-resolution x-ray scattering and x-ray photon correlation spectroscopy (XPCS), we have investigated the structure and dynamics of charge density wave (CDW) dynamics in pure and titanium-doped 1T-TaS2. Time-averaged scattering measurements of pure and doped samples reveal that 1T-TaS2 is a weakly pinned two-dimensional CDW system. Using XPCS, we find that after long anneals the CDW domain structure in the incommensurate phase is pinned and stable against spontaneous fluctuations thus rejecting phasons as spontaneous excitations in higher-dimensional CDW systems. By examining the dynamics of deeply quenched samples upon heating, we find that metastable CDW configurations collectively rearrange in a nonequilibrium manner. For nominally pure samples, we determine an energy barrier to relaxation of 4600 K that is considerably greater than that found for lower-dimensional CDWs. [ABSTRACT FROM AUTHOR]

Polymer electrolytes are promising materials for high energy density rechargeable batteries. However, they have low ion transport rates and gradually lose electrode adhesion during cycling. These effects are dependent on polymer structure and dynamics. This motivates an investigation of diblock copolymer electrolyte dynamics. Structural and stress relaxations have been measured with X-ray photon correlation spectroscopy (XPCS) and rheology, respectively, as a function of salt concentration and temperature. The polymer electrolyte studied in this work is a mixture of poly(styrene-b-ethylene oxide), SEO, and lithium bistrifluoromethanesulfonimide (LiTFSI). Results from XPCS experiments showed hyperdiffusive motion for various lithium salt concentrations and at varying temperatures, which is indicative of soft glassy materials. This behavior is attributed to cooperative dynamics. The decay time was a weak, nonmonotonic function of salt concentration and decreased with increasing temperature, in an Arrhenius fashion. In contrast, the shear modulus decreased with increasing salt concentration and increasing temperature. The entanglement relaxation from rheological measurements followed Vogel-Fulcher-Tammann behavior. The structural decay time was slower than the entanglement relaxation time at temperatures above the glass transition temperature, but they were approximately equal at Tg regardless of salt concentration. This may indicate a fundamental connection between cooperative structural motion and polymer chain motion in this material. [ABSTRACT FROM AUTHOR]

Recent measurements of the scattering function and of the dynamics of surface and interfacial fluctuations in thin supported molten films and bilayers using synchrotron X-ray diffuse scattering and photon correlation spectroscopy in reflection geometry are reported. The results for monolayer films thicker than four times of the radius of gyration of polystyrene show behavior of normal over-damped capillary waves expected for the surface fluctuations of a viscous liquid. However, thinner films show deviations indicating the need to account for viscoelasticity. The theory has been extended to the surface and interfacial modes in a bilayer film system. The results are discussed in terms of surface tension, viscosity and shear modulus. Also recent experiments to measure the isothermal compressibility of supported polystyrene films by studying `bulk' scattering from the interior of the films is discussed. [ABSTRACT FROM AUTHOR]

Abstract: The MPICorrelator application is a parallel application for processing multi-speckle X-ray photon correlation spectroscopy data via a data-parallelized implementation of the multi-tau algorithm. MPICorrelator spreads the analysis across a number of computing nodes in a cluster. Leveraging a number of computing nodes in this manner has led to a 30 times decrease in the amount of time required to analyze a multi-speckle time series. The system has recently gone operational at the 8 ID I beamline and has demonstrated the ability to keep up with acquisition rates of megapixel frames acquired at 60Hz. Future improvements will increase the analysis rate to allow for real-time operation and feedback on live acquired data. [Copyright &y& Elsevier]

The dynamics of concentrated suspensions of the eye-lens protein alpha crystallin have been measured using x-ray photon correlation spectroscopy. Measurements were made at wave vectors corresponding to the first peak in the hard-sphere structure factor and volume fractions close to the critical volume fraction for the glass transition. Langevin dynamics simulations were also performed in parallel to the experiments. The intermediate scattering function f(q,τ) could be fit using a stretched exponential decay for both experiments and numerical simulations. The measured relaxation times show good agreement with simulations for polydisperse hard-sphere colloids. [ABSTRACT FROM AUTHOR]