Highly stable petroleum pitches provide access to the deep glassy state.

Differential scanning calorimetry (DSC) was used to study the fast aging behavior of two petroleum pitch materials despite being only three to five years old. We observe that these highly aromatic pitches with broad distributions of both molecular weight and aromaticity exhibit large enthalpic relaxation endotherms in initial DSC heating scans, and 20-32 °C reductions in the fictive temperature and 0.35-0.87 of θK, which are indicative of aged glasses similar to ultrastable glasses and 20 MA aged amber. Quantifying the degree of thermodynamic stability relative to the Kauzmann temperature vs. the aging time demonstrates that these materials age just as quickly as low fragility metallic glasses. Additionally, we observe that pitches age faster than polymers reported in the literature when compared using down-jump experiments. We hypothesize that the fraction of higher aromaticity of pitch molecules plays a crucial role in faster dynamics. The unique aging behavior and the ability to produce pitches in bulk quantities using pilot-scale equipment, while being possible to tailor their molecular composition, make them a useful material for studying complex aging dynamics in the deep glassy state.

The effect of pyrolysis on the chemical, thermal and rheological properties of pitch.

Pitch-based carbon fibers are of considerable interest as high-performance materials. There are reports over the last several decades detailing (i) methods of improving pitch-based carbon fiber performance, and (ii) reducing the cost of production via novel processing techniques. However, there remain considerable challenges in producing high-performance pitch-based carbon fibers consistently on an industrial scale. This is arguably due to the difficulty of scaling the melt-spinning process to compensate for variability in pitch feedstock quality and a lack of understanding of processing-structure-performance relationships. This work focuses on the early stages of heat treatment (pyrolysis) of isotropic pitch and its effect on the chemical, thermal, and rheological properties of the pitch, which help determine its processability. More specifically, we quantify significant changes in chemical structure, Mw, Tg, Ts, and shear and extensional rheology as a function of pyrolysis time at 400 °C. The extensional rheology, in particular, shows that the 'stretchability' of the pitch samples strongly depends on pyrolysis severity, and is important for characterizing 'drawability'. Using a novel analysis of the uniaxial stretching kinematics, we show an isothermal 'drawability window' that allows for the largest axial and radial Hencky strains at constant rate. We hypothesize that this extensional drawability window could facilitate the successful processing of pitch into high quality fiber, minimizing the trial-and-error approach currently used in the field.

Large-scale synthesis of colloidal bowl-shaped particles.

We describe a general procedure for the large-scale fabrication of bowl-shaped colloidal particles using an emulsion templating technique. Following this method, single polymeric seed particles become located on individual oil droplet surfaces. The polymer phase is subsequently plasticized using an appropriate solvent. In this critical step, the compliant seed is deformed by surface tension, with the droplet serving as a templating surface. Solvent evaporation freezes the desired particle shape and the oil is subsequently removed by alcohol dissolution. The resulting uniformly-shaped colloidal particles were studied using scanning electron and optical microscopy. By adjusting the droplet size and the seed particle diameter, we demonstrate that the final particle shape can be controlled precisely, from shallow lenses to deep bowls. We also show that the colloid's uniformity and abundant quantity allowed the depletion-mediated assembly of flexible colloidal chains and clusters.

Colloidal Organosilica Spheres for Three-Dimensional Confocal Microscopy.

We describe the synthesis and application of 3-(trimethoxysilyl)propyl methacrylate (TPM) particles as a colloidal model system for three-dimensional (3D) confocal scanning laser microscopy. The effect of the initial TPM concentration on the growth and polydispersity of the particles and a recently developed solvent transfer method to disperse particles in a refractive index and density-matching solvent mixture are reviewed and discussed. To fully characterize the system as a colloidal model, we measure the pair potential between the TPM particles directly using optical tweezers. Finally, we use 3D confocal microscopy to image a sedimentation-diffusion equilibrium of TPM particles to characterize the phase behavior and particle dynamics through successful detection and tracking of all particles in the field of view.

Core-Shell Particles for Simultaneous 3D Imaging and Optical Tweezing in Dense Colloidal Materials.

A new colloidal system that consists of core-shell "probe" particles embedded in an optically transparent "host" particle suspension is developed. This system enables simultaneous fast confocal imaging and optical tweezing in dense 3D colloidal materials.

Digital colloids: reconfigurable clusters as high information density elements.

Through the design and manipulation of discrete, nanoscale systems capable of encoding massive amounts of information, the basic components of computation are open to reinvention. These components will enable tagging, memory storage, and sensing in unusual environments - elementary functions crucial for soft robotics and "wet computing". Here we show how reconfigurable clusters made of N colloidal particles bound flexibly to a central colloidal sphere have the capacity to store an amount of information that increases as O(N ln(N)). Using Brownian dynamics simulations, we predict dynamical regimes that allow for information to be written, saved, and erased. We experimentally assemble an N = 4 reconfigurable cluster from chemically synthesized colloidal building blocks, and monitor its equilibrium dynamics. We observe state switching in agreement with simulations. This cluster can store one bit of information, and represents the simplest digital colloid.

Brownian motion and the hydrodynamic friction tensor for colloidal particles of complex shape.

We synthesize colloidal particles with various anisotropic shapes and track their orientationally resolved Brownian trajectories using confocal microscopy. An analysis of appropriate short-time correlation functions provides direct access to the hydrodynamic friction tensor of the particles revealing nontrivial couplings between the translational and rotational degrees of freedom. The results are consistent with calculations of the hydrodynamic friction tensor in the low-Reynolds-number regime for the experimentally determined particle shapes.

Decoupling of rotational and translational diffusion in supercooled colloidal fluids.

We use confocal microscopy to directly observe 3D translational and rotational diffusion of tetrahedral clusters, which serve as tracers in colloidal supercooled fluids. We find that as the colloidal glass transition is approached, translational and rotational diffusion decouple from each other: Rotational diffusion remains inversely proportional to the growing viscosity whereas translational diffusion does not, decreasing by a much lesser extent. We quantify the rotational motion with two distinct methods, finding agreement between these methods, in contrast with recent simulation results. The decoupling coincides with the emergence of non-Gaussian displacement distributions for translation whereas rotational displacement distributions remain Gaussian. Ultimately, our work demonstrates that as the glass transition is approached, the sample can no longer be approximated as a continuum fluid when considering diffusion.

Influence of confinement on dynamical heterogeneities in dense colloidal samples.

We study a dense colloidal suspension confined between two quasiparallel glass plates as a model system for a supercooled liquid in confined geometries. We directly observe the three-dimensional Brownian motion of the colloidal particles using laser scanning confocal microscopy. The particles form dense layers along the walls, but crystallization is avoided as we use a mixture of two particle sizes. A normally liquidlike sample, when confined, exhibits slower diffusive motion. Particle rearrangements are spatially heterogeneous, and the shapes of the rearranging regions are strongly influenced by the layering. These rearranging regions become more planar upon confinement. The wall-induced layers and changing character of the spatially heterogeneous dynamics appear strongly connected to the confinement-induced glassiness.

Tracking rotational diffusion of colloidal clusters.

We describe a novel method of tracking the rotational motion of clusters of colloidal particles. Our method utilizes rigid body transformations to determine the rotations of a cluster and extends conventional proven particle tracking techniques in a simple way, thus facilitating the study of rotational dynamics in systems containing or composed of colloidal clusters. We test our method by measuring dynamical properties of simulated Brownian clusters under conditions relevant to microscopy experiments. We then use the technique to track and describe the motions of a real colloidal cluster imaged with confocal microscopy.

Large core-shell poly(methyl methacrylate) colloidal clusters: synthesis, characterization, and tracking.

We present a multistep procedure yielding large (diameter > 2 µm) monodisperse, fluorescently labeled core-shell poly(methyl methacrylate) (PMMA) latex particles via dispersion polymerization. The particles' physical properties were controlled by adjusting two reaction parameters, the initiator and chain transfer agent concentrations, which influence the molecular weight of the PMMA. Under certain conditions, particles with the requisite properties for fabricating colloidal clusters were synthesized. The resulting clusters represent a new type of nonspherical colloid that can be dispersed in a density- and refractive index-matching solvent, making them ideal for quantitative studies using confocal microscopy. To demonstrate the utility of our clusters, we measured the translational and rotational diffusion coefficients of a tetrahedral cluster by tracking the motion of its constituent particles in three-dimensional space. More broadly, our findings provide new insights concerning PMMA dispersion polymerization in apolar media.

Colloidal glass transition observed in confinement.

We study a colloidal suspension confined between two quasiparallel walls as a model system for glass transitions in confined geometries. The suspension is a mixture of two particle sizes to prevent wall-induced crystallization. We use confocal microscopy to directly observe the motion of colloidal particles. This motion is slower in confinement, thus producing glassy behavior in a sample which is a liquid in an unconfined geometry. For higher volume fraction samples (closer to the glass transition), the onset of confinement effects occurs at larger length scales.