Jyo Lyn Hor

Structure-property relationships from universal signatures of plasticity in disordered solids

Behavioral universality across size scales Glassy materials are characterized by a lack of long-range order, whether at the atomic level or at much larger length scales. But to what extent is their commonality in the behavior retained at these different scales? Cubuk et al. used experiments and simulations to show universality across seven orders of magnitude in length. Particle rearrangements in such systems are mediated by defects that are on the order of a few particle diameters. These rearrangements correlate with the materials softness and yielding behavior. Science, this issue p. 1033 A range of particle-based and glassy systems show universal features of the onset of plasticity and a universal yield strain. When deformed beyond their elastic limits, crystalline solids flow plastically via particle rearrangements localized around structural defects. Disordered solids also flow, but without obvious structural defects. We link structure to plasticity in disordered solids via a microscopic structural quantity, “softness,” designed by machine learning to be maximally predictive of rearrangements. Experimental results and computations enabled us to measure the spatial correlations and strain response of softness, as well as two measures of plasticity: the size of rearrangements and the yield strain. All four quantities maintained remarkable commonality in their values for disordered packings of objects ranging from atoms to grains, spanning seven orders of magnitude in diameter and 13 orders of magnitude in elastic modulus. These commonalities link the spatial correlations and strain response of softness to rearrangement size and yield strain, respectively.

Nanoporous Polymer-Infiltrated Nanoparticle Films with Uniform or Graded Porosity via Undersaturated Capillary Rise Infiltration

In this work, we present the fabrication of nanoporous polymer-infiltrated nanoparticle films (PINFs) with either uniform or graded porosity based on undersaturated capillary rise infiltration (UCaRI) and study the processing-structure-property relationship of these nanoporous PINFs. The UCaRI process involves first generating a bilayer film of a randomly packed nanoparticle layer atop a polymer layer, such that the volume of the polymer is less than the void volume in the nanoparticle packing. Subsequently, the bilayer film is annealed above the glass transition temperature of the polymer to induce polymer infiltration into the voids of the nanoparticle packing. Using in situ spectroscopic ellipsometry and molecular dynamics simulations, we observe that the polymer transport occurs in two stages: capillarity-induced infiltration, followed by gradual spreading, likely via surface diffusion. By varying the annealing time, UCaRI enables the generation of graded or uniform nanoporous PINFs. We also show that these nanoporous PINFs have tunable optical and mechanical properties, which can be tailored simply by changing the nanoparticle to polymer layer thickness ratio in the initial bilayer. The UCaRI approach is versatile and widely applicable to various polymers, which allows generation of nanoporous PINFs for multiple applications.

Disordered Nanoparticle Packings under Local Stress Exhibit Avalanche-Like, Environmentally Dependent Plastic Deformation

Nanoindentation experiments on disordered nanoparticle packings performed both in an atomic force microscope and in situ in a transmission electron microscope are used to investigate the mechanics of plastic deformation. Under an applied load, these highly porous films exhibit load drops, the magnitudes of which are consistent with an exponential population distribution. These load drops are attributed to local rearrangements of a small number of particles, which bear similarities to shear transformation zones and to the T1 process, both of which have been previously predicted for disordered packings. An increase in the relative humidity results in an increase in the number of observed load drops, indicating that the strength of the particle interactions has a significant effect on the modes of plastic deformation. These results suggest how disordered nanoparticle packings may be expected to behave in devices operating under varying environments.

Dramatic Increase in Polymer Glass Transition Temperature under Extreme Nanoconfinement in Weakly Interacting Nanoparticle Films

Properties of polymers in polymer nanocomposites and nanopores have been shown to deviate from their respective bulk properties due to physical confinement as well as polymer-particle interfacial interactions. However, separating the confinement effects from the interfacial effects under extreme nanoconfinement is experimentally challenging. Capillary rise infiltration enables polymer infiltration into nanoparticle (NP) packings, thereby confining polymers within extremely small pores and dramatically increasing the interfacial area, providing a good system to systematically distinguish the role of each effect on polymer properties. In this study, we investigate the effect of spatial confinement on the glass transition temperature ( Tg) of polystyrene (PS) infiltrated into SiO2 NP films. The degree of confinement is tuned by varying the molecular weight of polymers, the size of NPs (diameters between 11 and 100 nm, producing 3-30 nm average pore sizes), and the fill-fraction of PS in the NP films. We show that in these dense NP packings the Tg of confined PS, which interacts weakly with SiO2 NPs, significantly increases with decreasing pore size such that for the two molecular weights of PS studied the Tg increases by up to 50 K in 11 nm NP packings, while Tg is close to the bulk Tg in 100 nm NP packings. Interestingly, as the fill-fraction of PS is decreased, resulting in the accumulation of the polymer in the contacts between nanoparticles, hence an increased specific interfacial area, the Tg further increases relative to the fully filled films by another 5-8 K, indicating the strong role of geometrical confinement as opposed to the interfacial effects on the measured Tg values.