Microscopic origin of shear banding as a localized driven glass transition in compressed colloidal pillars.

Here we report on compression experiments of colloidal pillars in which the evolution of a shear band can be followed at the particle level during deformation. Quasistatic deformation results in dilation and anisotropic changes in coordination in a localized band of material. Additionally, a transition from solid- to liquidlike mechanical response accompanies the structural change in the band, as evidenced by saturation of the packing fraction at the glass transition point, a diminishing ability to host anelastic strains, and a rapid decay in the long-range strain correlations. Overall, our results suggest that shear banding quantitatively resembles a localized, driven glass transition.

Toughening Nanoparticle Films via Polymer Infiltration and Confinement.

Disordered nanoparticle films have significant technological applications as coatings and membranes. Unfortunately, their use to date has been limited by poor mechanical properties, notably low fracture toughness, which often results in brittle failure and cracking. We demonstrate that the fracture toughness of TiO2 nanoparticle films can be increased by nearly an order of magnitude through infiltration of polystyrene into the film. The fracture properties of films with various polymer volume fractions were characterized via nanoindentation pillar-splitting tests. Significant toughening is observed even at low volume fractions of polymer, which allows the nanoparticle packing to be toughened while retaining porosity. Moreover, higher-molecular-weight polymers lead to greater toughening at low polymer volume fractions. The toughness enhancement observed in polymer-infiltrated nanoparticle films may be attributed to multiple factors, including an increase in the area and strength of interparticle contacts, deflection and blunting of cracks during failure, and confinement-induced polymer bridging of nanoparticles. Our findings demonstrate that polymer infiltration is a highly effective route for reinforcing nanoparticle packings while retaining porosity.

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.

Effects of polymer-nanoparticle interactions on the viscosity of unentangled polymers under extreme nanoconfinement during capillary rise infiltration.

We explore the effect of confinement and polymer-nanoparticle interactions on the viscosity of unentangled polymers undergoing capillary rise infiltration (CaRI) in dense packings of nanoparticles. In CaRI, a polymer is thermally induced to wick into the dense packings of nanoparticles, leading to the formation of polymer-infiltrated nanoparticle films, a new class of thin film nanocomposites with extremely high concentrations of nanoparticles. To understand the effect of this extreme nanoconfinement, as well as polymer-nanoparticle interactions on the polymer viscosity in CaRI films, we use two polymers that are known to have very different interactions with SiO2 nanoparticles. Using in situ spectroscopic ellipsometry, we monitor the polymer infiltration process, from which we infer the polymer viscosity based on the Lucas-Washburn model. Our results suggest that physical confinement increases the viscosity by approximately two orders of magnitude. Furthermore, confinement also increases the glass transition temperature of both polymers. Thus, under extreme nanoconfinement, the physical confinement has a more significant impact than the polymer-nanoparticle interactions on the viscosity of unentangled polymers, measured through infiltration dynamics, as well as the glass transition temperature. These findings will provide fundamental frameworks for designing processes to enable the fabrication of CaRI nanocomposite films with a wide range of nanoparticles and polymers.

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.

Heterogeneity in the Small-Scale Deformation Behavior of Disordered Nanoparticle Packings.

Atomic force microscopy-based nanoindentation is used to image and probe the local mechanical properties of thin disordered nanoparticle packings. The probed region is limited to the size of a few particles, and an individual particle can be loaded and displaced to a fraction of a single particle radius. The results demonstrate heterogeneous mechanical response that is location-dependent. The weak locations may be analogous to the "soft spots" previously predicted in glasses and other disordered packings.

Polymer nanocomposite films with extremely high nanoparticle loadings via capillary rise infiltration (CaRI).

Polymer nanocomposite films (PNCFs) with extremely high concentrations of nanoparticles are important components in energy storage and conversion devices and also find use as protective coatings in various applications. PNCFs with high loadings of nanoparticles, however, are difficult to prepare because of the poor processability of polymer-nanoparticle mixtures with high concentrations of nanoparticles even at an elevated temperature. This problem is exacerbated when anisotropic nanoparticles are the desired filler materials. Here we report a straightforward method for generating PNCFs with extremely high loadings of nanoparticles. Our method is based on what we call capillary rise infiltration (CaRI) of polymer into a dense packing of nanoparticles. CaRI consists of two simple steps: (1) the preparation of a two-layer film, consisting of a porous layer of nanoparticles and a layer of polymer and (2) annealing of the bilayer structure above the temperature that imparts mobility to the polymer (e.g., glass transition of the polymer). The second step leads to polymer infiltration into the interstices of the nanoparticle layer, reminiscent of the capillary rise of simple fluid into a narrow capillary or a packing of granules. We use in situ spectroscopic ellipsometry and a three-layer Cauchy model to follow the capillary rise of polystyrene into the random network of nanoparticles. The infiltration of polystyrene into a densely packed TiO2 nanoparticle layer is shown to follow the classical Lucas-Washburn type of behaviour. We also demonstrate that PNCFs with densely packed anisotropic TiO2 nanoparticles can be readily generated by spin coating anisotropic TiO2 nanoparticles atop a polystyrene film and subsequently thermally annealing the bilayer film. We show that CaRI leads to PNCFs with modulus, hardness and scratch resistance that are far superior to the properties of films of the component materials. In addition, CaRI fills in cracks that may exist in the nanoparticle layer, leading to the healing of nanoparticle films and the formation of defect-free PNCFs. We believe this approach is widely applicable for the preparation of PNCFs with extremely high loading of nanoparticles and potentially provides a unique approach to study capillarity-induced transport of polymers under extreme confinement.