Dynamics and kinetics in soft matter physics, biology, and nanoscience frequently occur on fast (sub)microsecond but not ultrafast timescales which are difficult to probe experimentally. The European X-ray Free-Electron Laser (European XFEL), a megahertz hard X-ray Free-Electron Laser source, enables such experiments via taking series of diffraction patterns at repetition rates of up to 4.5 MHz. Here, we demonstrate X-ray photon correlation spectroscopy (XPCS) with submicrosecond time resolution of soft matter samples at the European XFEL. We show that the XFEL driven by a superconducting accelerator provides unprecedented beam stability within a pulse train. We performed microsecond sequential XPCS experiments probing equilibrium and nonequilibrium diffusion dynamics in water. We find nonlinear heating on microsecond timescales with dynamics beyond hot Brownian motion and superheated water states persisting up to 100 μs at high fluences. At short times up to 20 μs we observe that the dynamics do not obey the Stokes–Einstein predictions.

An X-ray cross-correlation study of the self-assembly of soft-shell nanoparticles is presented. It is demonstrated that the assembled films are structurally heterogeneous, with dominant hexagonal and cubic symmetries forming patches of 104–105 particles.

We investigate the out-of-equilibrium dynamics of a colloidal gel obtained by quenching a suspension of soft polymer-coated gold nanoparticles close to and below its gelation point using X-ray Photon Correlation Spectroscopy (XPCS).

Many soft-matter systems are composed of macromolecules or nanoparticles suspended in water. The characteristic times at intrinsic length scales of a few nanometres fall therefore in the microsecond and sub-microsecond time regimes. With the development of free-electron lasers (FELs) and fourth-generation synchrotron light-sources, time-resolved experiments in such time and length ranges will become routinely accessible in the near future. In the present work we report our findings on prototypical soft-matter systems, composed of charge-stabilized silica nanoparticles dispersed in water, with radii between 12 and 15 nm and volume fractions between 0.005 and 0.2. The sample dynamics were probed by means of X-ray photon correlation spectroscopy, employing the megahertz pulse repetition rate of the European XFEL and the Adaptive Gain Integrating Pixel Detector. We show that it is possible to correctly identify the dynamical properties that determine the diffusion constant, both for stationary samples and for systems driven by XFEL pulses. Remarkably, despite the high photon density the only observable induced effect is the heating of the scattering volume, meaning that all other X-ray induced effects do not influence the structure and the dynamics on the probed timescales. This work also illustrates the potential to control such induced heating and it can be predicted with thermodynamic models.

We study the structure and dynamics of colloidal particles with a spherical hard core and a thermo-responsive soft shell over the whole phase diagram by means of small-angle X-ray scattering and X-ray photon correlation spectroscopy. By changing the effective volume fraction by temperature and particle concentration, liquid, repulsive glass and attractive gel phases are observed. The dynamics slow down with increasing volume fraction in the liquid phase and reflect a Vogel-Fulcher-Tamann behaviour known for fragile glass formers. We find a liquid-glass transition above 50 vol.% that is independent from the particles' concentration and temperature. In an overpacked state at effective volume fractions above 1, the dispersion does not show a liquid phase but undergoes a gel-glass transition at an effective volume fraction of 34 vol.%. At the same concentration, extrema of subdiffusive dynamics are found in the liquid phase at lower weight fractions.We interpret this as dynamic precursors of the glass-gel transition.

We present the structure and dynamics of highly concentrated core–shell nanoparticles composed of a silica core and a poly­(N-isoproylacrylamide) (PNIPAm) shell suspended in water. With X-ray photon correlation spectroscopy, we are able to follow dynamical changes over the volume phase transition of PNIPAm at LCST = 32 °C. On raising the temperature beyond LCST, the structural relaxation times continue to decrease. The effect is accompanied by a transition from stretched to compressed exponential shape of the intensity autocorrelation function. Upon further heating, we find a sudden slowing down for the particles in their collapsed state. The q dependence of the relaxation time shows an anomalous change from τc ∝ q –3 to τc ∝ q –1. Small angle X-ray scattering data evidence a temperature-induced transition from repulsive to attractive forces. Our results indicate a temperature-induced phase transition from a colloidal liquid with polymer-driven dynamics toward a colloidal gel.

We study the structure and dynamics of aqueous dispersions of densely packed core–shell nanoparticles composed of a silica core and a poly(N-isoproylacrylamide) (PNIPAm) shell as a function of temperature and concentration.

An X-ray cross-correlation study of the local orientational order in selfassembled films made from PEGylated gold nanoparticles is presented. The local structure of this model system is dominated by four-and sixfold order. Coadsorption of shorter ligands in the particle's ligand layer and variation of salt concentration in the suspension prior to self-assembly result in a change of local orientational order. The degree of sixfold order is reduced after salt addition. This decrease of order is less pronounced for the fourfold symmetry. The results presented here suggest complex symmetry-selective order formation upon ligand exchange and salt addition and demonstrate the versatility of X-ray crosscorrelation methods for nanoparticle superlattices. research papers J. Appl. Cryst. (2019). 52, 777-782 Felix Lehmkü hler et al. Local orientational order in self-assembled nanoparticle films 781