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Jackson, Grayson L.

Publications and source records attributed to Jackson, Grayson L..

6 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Leveraging the Polymer Glass Transition to Access Thermally Switchable Shear Jamming Suspensions

Suspensions of polymeric nano-and microparticles are fascinating stress-responsive material systems that, depending on their composition, can display a diverse range of flow properties under shear, such as drastic thinning, thickening, and even jamming (reversible solidification driven by shear). However, investigations to date have almost exclusively focused on nonresponsive particles, which do not allow in situ tuning of the flow properties. Polymeric materials possess rich phase transitions that can be directly tuned by their chemical structures, which has enabled researchers to engineer versatile adaptive materials that can respond to targeted external stimuli. Reported herein are suspensions of (readily prepared) micrometer-sized polymeric particles with accessible glass transition temperatures (T g ) designed to thermally control their non-Newtonian rheology. The underlying mechanical stiffness and interparticle friction between particles change dramatically near T g . Capitalizing on these properties, it is shown that, in contrast to conventional systems, a dramatic and nonmonotonic change in shear thickening occurs as the suspensions transition through the particles' T g . This straightforward strategy enables the in situ turning on (or off) of the system's ability to shear jam by varying the temperature relative to T g and lays the groundwork for other types of stimuli-responsive jamming systems through polymer chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Designing Stress-Adaptive Dense Suspensions Using Dynamic Covalent Chemistry

The non-Newtonian behaviors of dense suspensions are central to their use in technological and industrial applications and arise from a network of particle–particle contacts that dynamically adapt to imposed shear. Reported herein are studies aimed at exploring how dynamic covalent chemistry between particles and the polymeric solvent can be used to tailor such stress-adaptive contact networks, leading to their unusual rheological behaviors. Specifically, a room temperature dynamic thia-Michael bond is employed to rationally tune the equilibrium constant (K eq ) of the polymeric solvent to the particle interface. It is demonstrated that low Keq leads to shear thinning, while high K eq produces antithixotropy, a rare phenomenon where the viscosity increases with shearing time. It is proposed that an increase in K eq increases the polymer graft density at the particle surface and that antithixotropy primarily arises from partial debonding of the polymeric graft/solvent from the particle surface and the formation of polymer bridges between particles. Thus, the implementation of dynamic covalent chemistry provides a new molecular handle with which to tailor the macroscopic rheology of suspensions by introducing programmable time dependence. These studies open the door to energy-absorbing materials that not only sense mechanical inputs and adjust their dissipation as a function of time or shear rate but also can switch between these two modalities on demand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ultrathin Porous Hydrocarbon Membranes Templated by Nanoparticle Assemblies

Porous polymer membranes are widely desired as catalyst supports, sensors, and active layers for separation membranes. We demonstrate that electron beam irradiation of freely suspended gold or Fe 3 O 4 nanoparticle (NP) monolayer sheets followed by wet chemical etching is a high-fidelity strategy to template two-dimensional (2D) porous crosslinked hydrocarbon membranes. This approach, which relies on secondary electrons generated by the NP cores, can further be used to transform three-dimensional (3D) terraced gold NP supercrystals into 3D porous hydrocarbon membranes. We utilize electron tomography to show how the number of NP layers (monolayer to pentalayer) controls attenuation and scattering of the primary e-beam, which in turn determines ligand crosslink density and 3D pore structure. Furthermore, electron tomography also reveals that many nanopores are vertically continuous due to preferential sintering of NPs. This work demonstrates new routes for the construction of functional nanoporous media.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Grain Growth and Coarsening Dynamics in a Compositionally Asymmetric Block Copolymer Revealed by X-ray Photon Correlation Spectroscopy

The dynamics of nanostructured soft materials crucially impact their associated macroscopic material properties, yet they are often difficult to measure due to spatiotemporal limitations of conventional instrumentation. Herein, we use X-ray photon correlation spectroscopy (XPCS) to directly observe particle-scale dynamics during grain growth and coarsening in a BCC- forming diblock polymer melt, with specific attention to the distribution of structural relaxation times associated with the interplanar (110) distance. Following sample quenching from the disordered state, these dynamical phenomena surprisingly exhibit little dependence on time and thermal quench depth. We posit that these relaxations stem from collective particle motions during grain rotation. We also observe unusual internally-referenced heterodyne correlations, which enable measurements of speed distributions within the sample. In this work, these speeds are significantly slower and appear at much longer annealing times than those previously reported during grain nucleation and growth in microphase separated block polymer melts. Drawing on analogies between polycrystalline hard and soft materials, we ascribe these speed distributions to misorientation-dependent grain boundary migration during ordered domain coarsening and anomalously fast, cooperative string-like particle motion along the grain boundaries. Thus, these coherent X-ray measurements provide new opportunities to interrogate grain boundary structure and dynamics in polycrystalline soft materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Consequences of Convex Nanopore Chemistry on Confined Water Dynamics

A basic understanding of confined water is crucial for developing selective ion transport and water purification membranes, yet the roles of nanopore geometry and functionality on confined water dynamics remain unresolved. We discuss the synthesis of perdeuterated ionic alkylsulfonate amphiphiles and their water-induced self-assembly into lyotropic liquid crystal (LLC) mesophases with well-defined, convex, sulfonate-lined nanopores. Quasielastic neutron scattering (QENS) measurements demonstrate that the water self-diffusion coefficients within these sulfonate-lined convex nanopores depend on the hydration level and amphiphile counterion identity (H + , K + , NMe 4 + ). The consistency of the observed counterion-dependent water dynamics trends with those of carboxylate LLCs is rationalized on the basis of similarities in the counterion spatial distributions in the water-filled channels, which we deduce from electron density maps derived from small-angle X-ray scattering (SAXS) analyses. These findings indicate that water diffusion is systematically faster in sulfonate-lined nanopores as compared to carboxylate-lined pores due to weaker water interactions with the softer and more hydrophobic–SO 3 – functionalities. These molecular-level insights into the relationships between convex pore wall chemical functionalities, hydrated counterions, and confined water diffusion may inform future development of new nanoporous media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗