In situ characterization by SAXS of concentration polarization layers during cross-flow ultrafiltration of Laponite dispersions.

The structural organization inside the concentration polarization layer during cross-flow membrane separation process of Laponite colloidal dispersions has been characterized for the first time by in situ time-resolved small-angle X-ray scattering (SAXS). Thanks to the development of new "SAXS cross-flow filtration cells", concentration profiles have been measured as a function of the distance z from the membrane surface with 50 µm accuracy and linked to the permeation flux, cross-flow, and transmembrane pressure registered simultaneously. Different rheological behaviors (thixotropic gel with a yield stress or shear thinning sol) have been explored by controlling the mutual interactions between the particles as a result on the addition of peptizer. The structural reversibility of the concentration polarization layer has been demonstrated being in agreement with permeation flux measurements. These observations were related to structure of the dispersions under flow and their osmotic pressure.

Competing interactions in arrested States of colloidal clays.

Using experiments, theory and simulations, we show that the arrested state observed in a colloidal clay at high concentrations is stabilized by screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to distinguish this disconnected state, which melts upon addition of water, from a low-concentration gel state, which does not melt. Theoretical modeling and simulations at high concentrations reproduce the measured small angle x-ray scattering static structure factors and confirm the long-range electrostatic nature of the arrested structure. These findings are attributed to the different time scales controlling the competing attractive and repulsive interactions.

Temperature Unmasks Allosteric Propensity in a Thermophilic Malate Dehydrogenase via Dewetting and Collapse.

In this work, we combine experiments and molecular simulations to unveil the hidden allosteric propensity of a thermophilic malate dehydrogenase protein (MDH). We provide evidence that, at its working temperature, the nonallosteric MDH takes a compact structure because of internal dewetting and reorganizes the active state toward functional conformations similar to its homologous allosteric LDHs. Moreover, a single-point mutation confers on the MDH a cooperative behavior that mimics an allosteric LDH. Our work not only demonstrates that thermophilic MDHs use temperature as an external parameter to regulate its functionality in a similar way allosteric LDHs use substrates/cofactors binding but also shows that the scaffold of MDHs possesses an intrinsic and hidden allosteric potentiality.

Probing the transverse coherence of an undulator x-ray beam using brownian particles.

We present a novel method to map the two-dimensional transverse coherence of an x-ray beam using the dynamical near-field speckles formed by scattering from colloidal particles. Owing to the statistical nature of the method, the coherence properties of synchrotron radiation from an undulator source is obtained with high accuracy. The two-dimensional complex coherence function is determined at the sample position and the imaging optical scheme further allowed us to evaluate the coherence factor at the undulator output despite the aberrations introduced by the focusing optics.

Correlation between structure and rheology of a model colloidal glass.

The microstructure and rheological properties of a model colloidal system was probed in the vicinity of the glass transition by small-angle and ultra small-angle x-ray scattering, dynamic light scattering (DLS) and bulk rheology. The volume fraction of the particles was deduced by modeling the structure factor and the absolute scattered intensity in a self-consistent way. The glass transition (phi(G)) was identified from the frequency dependence of the shear moduli in the linear regime. The experimentally observed behavior was then compared with the viscoelastic properties derived from mode-coupling theory (MCT) using the experimental structure factor as input to the theory. The ensemble-averaged intermediate scattering functions from DLS measurements were also compared with those calculated from the MCT and reasonable agreement was obtained.

Arrested state of clay-water suspensions: gel or glass?

The aging of a charged colloidal system has been studied by small-angle x-ray scattering, in the exchanged momentum range Q=0.03-5 nm(-1) , and by dynamic light scattering, at different clay concentrations (C(w)=0.6-2.8%) . The static structure factor S(Q) has been determined as a function of both aging time and concentration. This is the direct experimental evidence of the existence and evolution with aging time of two different arrested states in a single system simply obtained only by changing its volume fraction: an inhomogeneous state is reached at low concentrations, while a homogeneous one is found at high concentrations.

Kinetic arrest and glass-glass transition in short-ranged attractive colloids.

A thermally reversible repulsive hard-sphere to sticky-sphere transition was studied in a model colloidal system over a wide volume fraction range. The static microstructure was obtained from high resolution small angle x-ray scattering, the colloid dynamics was probed by dynamic x-ray and light scattering, and supplementary mechanical properties were derived from bulk rheology. At low concentration, the system shows features of gas-liquid type phase separation. The bulk phase separation is presumably interrupted by a gelation transition at the intermediate volume fraction range. At high volume fractions, fluid-attractive glass and repulsive glass-attractive glass transitions are observed. It is shown that the volume fraction of the particles can be reliably deduced from the absolute scattered intensity. The static structure factor is modeled in terms of an attractive square-well potential, using the leading order series expansion of Percus-Yevick approximation. The ensemble-averaged intermediate scattering function shows different levels of frozen components in the attractive and repulsive glassy states. The observed static and dynamic behavior are consistent with the predictions of a mode-coupling theory and numerical simulations for a square-well attractive system.

Ultrasonic assisted cross-flow ultrafiltration of starch and cellulose nanocrystals suspensions: characterization at multi-scales.

This study investigates for the first time the behaviors of starch and cellulose nanocrystals (SNC and CNC) suspensions which are simultaneously subjected to pressure, shear flow and ultrasound (US) during cross-flow ultrafiltration. This multi-forces process was characterized from macro-scales to nano-scales, with a custom designed "SAXS Cross-Flow US-coupled Filtration Cell". In addition, rheological behaviors of SNC samples at different concentrations/temperatures have been investigated. In both cases (ultrafiltration of SNC and CNC suspensions), better performances were observed with US. The in-situ SAXS measurements revealed that for SNC suspensions, no structure change occurred at the length scales range from 10 to 60nm in this multi-forces process, while CNC particles exhibited an ordered arrangement within the concentrated layer during the same process. SNC particles accumulated on the membrane surface forming a "fragile" concentrated layer which was removed very quickly by subsequent applied US. In contrary, the CNC particles accumulation was very severe, the additional ultrasonic force led to a disruption but not a totally removal of the CNC concentrated layer.

Calculation of scattering-patterns of ordered nano- and mesoscale materials.

Analytical expressions for the scattering patterns of ordered nano- and mesoscopic materials are derived and compared to measured scattering patterns. Ordered structures comprising spheres (fcc, bcc, hcp, sc, and bct), cylinders (hex and sq), lamellae (lam) and vesicles, as well as bicontinuous cubic structures (Ia3d, Pn3m, and Im3m) are considered. The expressions take into account unit cell dimensions, particle sizes and size distributions, lattice point deviations, finite domain sizes, orientational distributions, core/shell-structures as well a variety of peak shapes. The expressions allow to quantitatively describe, model and even fit measured SAXS and SANS-patterns of ordered or oriented micellar solutions, lyotropic phases, block copolymers, colloidal solutions, nanocomposites, photonic crystals, as well as mesoporous materials.

Kinetics of the X-ray induced gold nanoparticle synthesis.

Time resolved small angle scattering has been employed to follow the formation kinetics of gold nanoparticles from a solution of gold hydrochlorate and tris-sodium citrate at room temperature. While UV irradiation leads to a slow kinetics as observed by optical spectroscopy, the irradiation by the X-rays led to a reduction of the gold within a few minutes. The size and morphology evolution during the radiolytic formation of particles displays the initial nucleation phase and the growth kinetics, which exhibit very nonuniform behavior. They show that the electrostatics of the particle stabilization plays a pronounced role in the repulsive forces and transient clustering of particles.

Evidence for nanoparticles in microwave-generated fireballs observed by synchrotron x-ray scattering.

The small-angle x-ray scattering method has been applied to study fireballs ejected into the air from molten hot spots in borosilicate glass by localized microwaves [V. Dikhtyar and E. Jerby, Phys. Rev. Lett. 96 045002 (2006)10.1103/PhysRevLett.96.045002]. The fireball's particle size distribution, density, and decay rate in atmospheric pressure were measured. The results show that the fireballs contain particles with a mean size of approximately 50 nm with average number densities on the order of approximately 10(9). Hence, fireballs can be considered as a dusty plasma which consists of an ensemble of charged nanoparticles in the plasma volume. This finding is likened to the ball-lightning phenomenon explained by the formation of an oxidizing particle network liberated by lightning striking the ground [J. Abrahamson and J. Dinniss, Nature (London) 403, 519 (2000)10.1038/35000525].

Spatial and temporal in situ evolution of the concentration profile during casein micelle ultrafiltration probed by small-angle X-ray scattering.

Understanding the mechanisms involved in structural development in the vicinity of membrane constitutes a considerable challenge in the improvement of ultrafiltration process in industrial applications. In situ small-angle X-ray scattering (SAXS) performed with custom-made ultrafiltration cell has permitted the structural arrangement to be probed and concentration profiles to be obtained in deposited layers during frontal filtration of casein micelle suspension. SAXS allowed the structure of the accumulated layers of casein micelles between 280 microm and 1 mm from the membrane surface to be followed at length scales from a few nanometers to about 100 nm. These results have been combined with hydrodynamic measurements (permeation flux) and rheological investigations. Under frontal filtration, the time dependence of concentration at different distances from the membrane surface has been obtained. This temporal evolution is marked by an exponential increase of the concentration followed by a slower growth which has been associated with a change in the rheological behavior of the suspension from Newtonian to shear thinning behavior.

Microstructure and rheology near an attractive colloidal glass transition.

Microstructure and rheological properties of a thermally reversible short-ranged attractive colloidal system are studied in the vicinity of the attractive glass transition line. At high volume fractions, the static structure factor changes very little but the low frequency shear moduli varies over several orders of magnitude across the transition. From the frequency dependence of shear moduli, fluid-attractive glass and repulsive glass-attractive glass transitions are identified.

Direct determination of strain and composition profiles in SiGe islands by anomalous x-Ray diffraction at high momentum transfer.

Anomalous x-ray scattering is employed for quantitative measurements of the Ge composition profile in islands on Si(001). The anomalous effect in SiGe is enhanced exploiting the dependence of the complex atomic form factors on the momentum transfer. Comparing the intensity ratios for x-ray energies below and close to the K edge of Ge at various Bragg reflections in the grazing incidence diffraction setup, the sensitivity for the Ge profile is considerably enhanced. The method is demonstrated for SiGe dome-shaped islands grown on Si(001). It is found that the composition inside the island changes rather abruptly, whereas the lattice parameter relaxes continuously.