Phase stability and dynamics of entangled polymer-nanoparticle composites.

Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host

Electroconvective flow in presence of polyethylene glycol oligomer additives

Metal electrodeposition in batteries is fundamentally unstable and affected by different instabilities depending on operating conditions and chemical composition. Particularly at high charging rates, a hydrodynamic instability called electroconvection sets in that aggravates the situation by creating non-uniform ion flux and preferential deposition at the electrode. Here, we experimentally investigate how oligomer additives interact with the hydrodynamic instability at a cation selective interface. From electrochemical measurements and direct visualization experiments, we find that electroconvection is delayed and suppressed at all voltage in the presence of oligomers. Our results also reveal that it is important to consider the role of polymers at the interface, in addition to their bulk effects, to understand the stabilization effect and its mechanism

Flow field visualization of entangled polybutadiene solutions under nonlinear viscoelastic flow conditions

Using self-designed particle visualization instrumentation, startup shear and step-strain tests were conducted under a series of systematically varied rheological and geometrical conditions, and the velocity profiles in three different well-entangled polybutadiene/oligomer solutions were obtained. For startup shear tests, in the regime of entanglement densities up to 89 and nominal reptation Weissenberg numbers up to 18.6, we generally observe either wall slip and a linear velocity/strain profile or simply the linear profile with no wall slip unless a massive edge fracture or instability has occurred in the sample. Meanwhile, step-strain tests conducted at similar and higher step Weissenberg numbers revealed little particle motion upon cessation. These results lead us to a conclusion that there is no compelling evidence of shear banding or nonquiescent relaxation in the range of entanglement density and Wi investigated; we interpret the results to imply that any observed banding probably correlates with edge effects.National Science Foundation (U.S.) (Grant DMR-0934305

Characterization of Sulfur and Nanostructured Sulfur Battery Cathodes in Electron Microscopy Without Sublimation Artifacts

Lithium sulfur (Li-S) batteries have the potential to provide higher energy storage density at lower cost than conventional lithium ion batteries. A key challenge for Li-S batteries is the loss of sulfur to the electrolyte during cycling. This loss can be mitigated by sequestering the sulfur in nanostructured carbon-sulfur composites. The nanoscale characterization of the sulfur distribution within these complex nanostructured electrodes is normally performed by electron microscopy, but sulfur sublimates and redistributes in the high vacuum conditions of conventional electron microscopes. The resulting sublimation artifacts render characterization of sulfur in conventional electron microscopes problematic and unreliable. Here, we demonstrate two techniques, cryogenic transmission electron microscopy (cryo-TEM) and scanning electron microscopy in air (airSEM), that enable the reliable characterization of sulfur across multiple length scales by suppressing sulfur sublimation. We use cryo-TEM and airSEM to examine carbon-sulfur composites synthesized for use as Li-S battery cathodes, noting several cases where the commonly-employed sulfur melt infusion method is highly inefficient at infiltrating sulfur into porous carbon hosts

The Sabatier principle for Battery Anodes: Chemical Kinetics and Reversible Electrodeposition at Heterointerfaces

How surface chemistry influences reactions occurring thereupon has been a long-standing question of broad scientific and technological interest for centuries. Recently, it has re-emerged as a critical question in a subdiscipline of chemistry - electrochemistry at heterointerphases, where the answers have implications for both how, and in what forms, humanity stores the rising quantities of renewable electric power generated from solar and wind installations world-wide. Here we consider the relation between the surface chemistry at such interphases and the reversibility of electrochemical transformations at a rechargeable battery electrode. Conventional wisdom holds that stronger chemical interaction between the metal deposits and electrode promotes reversibility. We report instead that a moderate strength of chemical interaction between the deposit and the substrate, neither too weak nor too strong, enables highest reversibility and stability of the plating/stripping redox processes at a battery anode. Analogous to the empirical Sabatier principle for chemical heterogeneous catalysis, our finding arises from the confluence of competing processes - one driven by electrochemistry and the other by chemical alloying. Based on experimental evaluation of metal plating/stripping systems in battery anodes of contemporary interest, we show that such knowledge provides a powerful tool for designing key materials in highly reversible electrochemical energy storage technologies based on earth-abundant, low-cost metals.Comment: 64 pages. Initially submitted on March 16th, 2021; revised version submitted on November 14th, 2021 to the same Journa

Spontaneous sharp bending of DNA: role of melting bubbles

The role of centrally located and distributed base pair mismatches (‘melting bubbles’) on localized bending and stiffness of short dsDNA fragments is evaluated using time-dependent fluorescence lifetime measurements. Distributed melting bubbles are found to induce larger bending angles and decreased levels of stiffness in DNA than centrally located ones of comparable overall size. Our results indicate that spontaneous local opening-up of the DNA duplex could facilitate sharp bending of short DNA strands even in the absence of DNA binding proteins. We also find that the occurrence of two closely spaced melting bubbles will generally be favored when a large energetic barrier must be overcome in forming the desired bent DNA structure

“Fracture” phenomena in shearing flow of viscous liquids

In start-up of steady shearing flow of two viscous unentangled liquids, namely low-molecular-weight polystyrene and α-D-glucose, the shear stress catastrophically collapses if the shear rate is raised above a value corresponding to a critical initial shear stress of around 0.1–0.3 MPa. The time dependence of the shear stress during this process is similar for the two liquids, but visualization of samples in situ and after quenching reveals significant differences. For α-D-glucose, the stress collapse evidently results from debonding of the sample from the rheometer tool, while in polystyrene, bubbles open up within the sample, as occurs in cavitation. Some similarities are pointed out between these phenomena and that of “lubrication failure” reported in the tribology literature.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47212/1/397_2004_Article_BF00368135.pd