Increasing ionic conductivity within thermoplastics via commercial additives results in a dramatic decrease in fiber diameter from melt electrospinning.

Polyethylene melt conductivity was increased by adding a commercial anti-static agent, which resulted in a 20× decrease in electrospun fiber diameter and formation of a significant fraction of sub-micron diameter fibers. Two polyethylene formulations and varying additive concentrations were utilized to span the parameter space of conductivity and viscosity. The key role of conductivity in determining the jet radius (which sets the upper limit on the fiber size) is discussed in the context of fluid mechanics theory and previous simulations. Parameters which affect the conversion of the liquid jet to a solid fiber and the pertinent theory are outlined. An "unconfined" experimental configuration is utilized to both avoid potential needle clogging and enable direct observation of important characteristic length scales related to the interaction of the fluid and the applied electric field. In this approach, the fluid spontaneously forms an array of cone perturbations which act as stationary "nozzles" through which the mobile fluid flows to form the jet. The experimental data and theory considerations allow for a holistic discussion of the interaction between flow rate, viscosity, conductivity, and the resultant jet and fiber size. Information about the fluid viscosity and conductivity gained by observing the electrospinning process is highlighted. Schemes for theoretically predicting the cone-jet density, cone size, and flow rate are compared to experimental results.

Nanoparticle-based photothermal heating to drive chemical reactions within a solid: using inhomogeneous polymer degradation to manipulate mechanical properties and segregate carbonaceous by-products.

Photothermal heating via metal nanoparticles is utilized to degrade polyethylcyanoacrylate (PECA), which undergoes a thermally-driven depolymerization process, resulting in (i) monomer loss from the sample, (ii) repolymerization to form shorter chains (oligomer), and (iii) formation of carbonaceous by-products which are graphene-like and luminescent. These unique PECA properties are used to demonstrate the heterogeneous temperature distribution present during photothermal processing and the results are compared to degradation via conventional methods where a uniform temperature is present. Photothermal heating results in formation of pockets of depolymerized material around each nanoscale heating site. The characteristic size of these photothermally-generated mechanical defects is determined from changes in the material's tensile strength. Changes in mass loss and molecular weight are utilized to determine the fraction of the sample that has depolymerized: distributing this volume equally to each heating site (based on the nanoparticle concentration) results in a volume that matches the defect size from independent mechanical measurements. In this way, macroscopic measurements elucidate the mesoscopic pattern of photothermal degradation. Sample morphology on scales from millimeters to nanometers is assessed via optical and electron microscopy. The carbonaceous by-products of degradation form in the hot region around each nanoparticle during photothermal heating, as revealed by transmission electron microscopy studies. Heterogeneous heating is also evident from optical images where starch granules, employed as an inert dilute additive to enhance PECA mechanical properties, also become luminescent due to degradation in "hot spots" created by the overlap of warm regions from nearby nanoparticle sites. Beyond the fundamental knowledge gained by these studies, the results demonstrate the ability to manipulate the connection between mechanical properties and chemical degradation which is important for developing new strategies for management of polymeric waste.

Photothermally-driven thermo-oxidative degradation of low density polyethylene: heterogeneous heating plus a complex reaction leads to homogeneous chemistry.

Photothermal heating from embedded nanoparticles, a process whereby visible light is converted into heat resulting in a high temperature in each particle's immediate vicinity, was utilized to degrade low density polyethylene (LDPE) via thermo-oxidation. The spatially-varying steady-state photothermal temperature field is a potential mechanism by which ambient light (e.g. sunlight) could be used to drive chemical reactions within solid materials and may result in a non-uniform pattern of products, an advantage or disadvantage depending on application. Novel approaches to control polymer degradation are of interest because of the goal of remediating plastic waste, including autonomous means to minimize its effect when unconfined in the environment. For thermoplastic auto-oxidation, heterogeneous degradation would likely enhance deleterious micro-fragmentation however, the multi-step, multi-site nature of the reaction mitigated the temperature non-uniformity. A photothermally-heated LDPE nanocomposite with silver nanoparticle and cobalt-stearate additives showed degradation, characterized by ultraviolet-visible and Fourier-transform infrared absorption spectroscopy, electron microscopy, and mechanical testing, nearly identical to that resulting from uniform conventional treatment at the same average temperature.

Nanoscale steady-state temperature gradients within polymer nanocomposites undergoing continuous-wave photothermal heating from gold nanorods.

Anisotropically-shaped metal nanoparticles act as nanoscale heaters via excitation of a localized surface plasmon resonance, utilizing a photothermal effect which converts the optical energy into local heat. Steady-state temperatures within a polymer matrix embedded with gold nanorods undergoing photothermal heating using continuous-wave excitation are measured in the immediate spatial vicinity of the nanoparticle (referred to as the local temperature) from observing the rate of physical rotation of the asymmetric nanoparticles within the locally created polymer melt. Average temperatures across the entire (mostly solid) sample (referred to as the global temperature) are simultaneously observed using a fluorescence method from randomly dispersed molecular emitters. Comparing these two independent measurements in films having varying concentrations of nanorods reveals the interplay between the local and global temperatures, clearly demonstrating the capability of these material samples to sustain large steady-state spatial temperature gradients when experiencing continuous-wave excitation photothermal heating. These results are discussed quantitatively. Illustrative imaging studies of nanofibers under photothermal heating also support the presence of a large temperature gradient. Photothermal heating in this manner has potential utility in creating unique thermal processing conditions for outcomes such as driving chemical reactions, inducing crystallinity changes, or enhancing degradation processes in a manner unachievable by conventional heating methods.

Spatial temperature mapping within polymer nanocomposites undergoing ultrafast photothermal heating via gold nanorods.

Heat emanates from gold nanorods (GNRs) under ultrafast optical excitation of the localized surface plasmon resonance. The steady state nanoscale temperature distribution formed within a polymer matrix embedded with GNRs undergoing pulsed femtosecond photothermal heating is determined experimentally using two independent ensemble optical techniques. Physical rotation of the nanorods reveals the average local temperature of the polymer melt in the immediate spatial volume surrounding each rod while fluorescence of homogeneously-distributed perylene molecules monitors temperature over sample regions at larger distances from the GNRs. Polarization-sensitive fluorescence measurements of the perylene probes provide an estimate of the average size of the quasi-molten region surrounding each nanorod (that is, the boundary between softened polymer and solid material as the temperature decreases radially away from each particle) and distinguishes the steady state temperature in the solid and melt regions. Combining these separate methods enables nanoscale spatial mapping of the average steady state temperature distribution caused by ultrafast excitation of the GNRs. These observations definitively demonstrate the presence of a steady-state temperature gradient and indicate that localized heating via the photothermal effect within materials enables nanoscale thermal manipulations without significantly altering the bulk sample temperature in these systems. These quantitative results are further verified by re-orienting nanorods within a solid polymer nanofiber without inducing any morphological changes to the highly temperature-sensitive nanofiber surface. Temperature differences of 70-90 °C were observed over a distances of ∼ 100 nm.

Dynamics within alkylsiloxane self-assembled monolayers studied by sensitive dielectric spectroscopy.

Self-assembled monolayers are a ubiquitous laboratory tool and have been the subject of many experimental investigations which have primarily focused on static properties of full coverage monolayers, with the maximum density and ordering possible. In this work, dynamics within low density, planar siloxane self-assembled monolayers are studied utilizing highly sensitive dielectric spectroscopy. Dilute, disordered films were intentionally fabricated in order to study the widest range of possible motions. At low coverage, an interacting relaxation is observed, which has similar dynamics to polyethylene-like glass transitions observed in phase-segregated side-chain polymers, despite the rigidity of the substrate and the constraint of ethyl groups in relatively short chains. As density is increased, a second local relaxation, previously observed in three-dimensional SAMs and associated with rotation within a small segment of the alkyl chain, is also observed.