Imaging the Molecular Motions of Autonomous Repair in a Self‐Healing Polymer

Self‐healing polymers can significantly extend the service life of materials and structures by autonomously repairing damage. Intrinsic healing holds great promise as a design strategy to mitigate the risks of damage by delaying or preventing catastrophic failure. However, experimentally resolving the microscopic mechanisms of intrinsic repair has proven highly challenging. This work demonstrates how optical micromechanical mapping enables the quantitative imaging of these molecular‐scale dynamics with high spatiotemporal resolution. This approach allows disentangling delocalized viscoplastic relaxation and localized cohesion‐restoring rebonding processes that occur simultaneously upon damage to a self‐healing polymer. Moreover, frequency‐ and temperature‐dependent imaging provides a way to pinpoint the repair modes in the relaxation spectrum of the quiescent material. These results give rise to a complete picture of autonomous repair that will guide the rational design of improved self‐healing materials.     

Citrate‐Induced Nanocubes: A Re‐Examination of the Role of Citrate as a Shape‐Directing Capping Agent for Ag‐Based Nanostructures

Seed‐mediated syntheses utilizing facet‐selective surface passivation provide the necessary chemical controls to direct noble metal nanostructure formation to a predetermined geometry. The foremost protocol for the synthesis of (111)‐faceted Ag octahedra involves the reduction of metal ions onto pre‐existing seeds in the presence of citrate and ascorbic acid. It is generally accepted that the capping of (111) facets with citrate dictates the shape while ascorbic acid acts solely as the reducing agent. Herein, a citrate‐based synthesis is demonstrated in which the presence or absence of ascorbic acid is the shape‐determining factor. Reactions are carried out in which Ag⁺ ions are reduced onto substrate‐immobilized Ag, Au, Pd, and Pt seeds. Syntheses lacking ascorbic acid, in which citrate acts as both the capping and the reducing agent, result in a robust nanocube growth mode able to withstand wide variations in the concentration of reactants, reaction rates, seed material, seed orientation and faceting, pH, and substrate material. If, however, ascorbic acid is included in these syntheses, then the growth mode reverts to one that advances the octahedral geometry. The implication of these results is that citrate, or one of its oxidation products, selectively caps (100) facets, but where this capability is compromised by ascorbic acid.     

Temperature‐Enhanced Solvent Vapor Annealing of a C3 Symmetric Hexa‐peri‐Hexabenzocoronene: Controlling the Self‐Assembly from Nano‐ to Macroscale

Temperature‐enhanced solvent vapor annealing (TESVA) is used to self‐assemble functionalized polycyclic aromatic hydrocarbon molecules into ordered macroscopic layers and crystals on solid surfaces. A novel C₃ symmetric hexa‐peri‐hexabenzocoronene functionalized with alternating hydrophilic and hydrophobic side chains is used as a model system since its multivalent character can be expected to offer unique self‐assembly properties and behavior in different solvents. TESVA promotes the molecule's long‐range mobility, as proven by their diffusion on a Si/SiO_x surface on a scale of hundreds of micrometers. This leads to self‐assembly into large, ordered crystals featuring an edge‐on columnar type of arrangement, which differs from the morphologies obtained using conventional solution‐processing methods such as spin‐coating or drop‐casting. The temperature modulation in the TESVA makes it possible to achieve an additional control over the role of hydrodynamic forces in the self‐assembly at surfaces, leading to a macroscopic self‐healing within the adsorbed film notably improved as compared to conventional solvent vapor annealing. This surface re‐organization can be monitored in real time by optical and atomic force microscopy.     

Na‐Cation‐Assisted Exfoliation of MX2 (M = Mo,W; X = S,Se) Nanosheets in an Aqueous Medium with the Aid of a Polymeric Surfactant for Flexible Polymer‐Nanocomposite Memory Applications

2D nanosheets of transition metal dichalcogenides (TMDCs) have been attracting attention due to their sizable band gap. Facile and effective Na‐cation‐assisted exfoliation of TMDC (MX₂, M = Mo, W; X = S, Se) nanosheets in an aqueous medium and their application as a composite filler in a polyvinyl alcohol (PVA) matrix are explored in this work. The presence of Na cations is highly beneficial for exfoliating defect‐free and few‐layer MX₂ nanosheets in water in the presence of small‐sized micelles of polymeric surfactant, and significantly elevates the exfoliation yield by more than one order of magnitude compared to a conventional surfactant‐assisted exfoliation. The strategy suggested in this work is very advantageous compared to both Li cation intercalation in organic solvents and conventional low‐yield surfactant‐assisted exfoliations. As an application of the exfoliated nanosheets, the fabrication of memory devices with the configuration of Ga‐doped ZnO/MX₂–PVA/Ag is demonstrated, and they exhibit bistable and write‐once‐read‐many‐times resistive switching behavior with a high ON/OFF current ratio of 3 × 10³ at ?1.0 V (for WS₂) and 2.0 V (for MoS₂). Furthermore, MX₂–PVA nanocomposite fibrous films and mats are successfully fabricated using an electrospinning technique, which can expand the use of TMDC nanofillers in applications involving highly flexible polymer‐based MX₂ composites.     

Chemical Vapor Deposition of Bernal‐Stacked Graphene on a Cu Surface by Breaking the Carbon Solubility Symmetry in Cu Foils

The synthesis of Bernal‐stacked multilayer graphene over large areas is intensively investigated due to the value of this material's tunable electronic structure, which makes it promising for use in a wide range of optoelectronic applications. Multilayer graphene is typically formed via chemical vapor deposition onto a metal catalyst, such as Ni, a Cu–Ni alloy, or a Cu pocket. These methods, however, require sophisticated control over the process parameters, which limits the process reproducibility and reliability. Here, a new synthetic method for the facile growth of large‐area Bernal‐stacked multilayer graphene with precise layer control is proposed. A thin Ni film is deposited onto the back side of a Cu foil to induce controlled diffusion of carbon atoms through bulk Cu from the back to the front. The resulting multilayer graphene exhibits a 97% uniformity and a sheet resistance of 50 Ω sq^?1 with a 90% transmittance after doping. The growth mechanism is elucidated and a generalized kinetic model is developed to describe Bernal‐stacked multilayer graphene growth by the carbon atoms diffused through bulk Cu.     

Monitoring the Condition of Non‐linear Packaging Materials Subject to Varying Excitation Levels Using a Reverse Multiple Input/Single Output Based Approach

During transportation, protective packaging is subjected to random dynamic compressive loads that arise from random vibrations generated by the vehicle. The ability of the protective packaging to withstand these dynamic compressive loads depends on the environmental vibration levels, the nominal stresses and the material's characteristics. Previous research has shown that cumulative damage, in the packaging system under random dynamic compression, will result in a change in the overall stiffness of the system. This change is manifested as a shift in the system's fundamental resonant frequency. Natural frequency estimates are often extracted using a least squares regression curve fit applied to an estimate of the system's frequency response function. Frequency response function estimates are generally obtained using the Fourier transform with a single input/single output (SISO). This approach is suitable for many applications; however, it is not well suited to non‐linear systems subjected to non‐stationary excitation where the vibration level (overall root‐mean‐square value) can vary. This paper investigates the use of an optimised reverse multiple input/single output algorithm for reliably tracking variations in the condition of packaging elements subjected to excitation with varying magnitude (root‐mean‐square). Results are presented from the analysis of physical experiments performed on expanded polystyrene cushions as well as empty corrugated paperboard containers. The experiments performed using the polystyrene samples were designed to limit natural variation in the system's natural frequency; whereas the paperboard samples were allowed to naturally damage under dynamic loading. Copyright © 2015 John Wiley & Sons, Ltd.     

Observation of the Dissolution of Topologically Close Packed Phases by an Additional Heat Treatment in Third Generation Nickel‐Based Single Crystal Superalloy Turbine Blades

Topologically close packed (TCP) phases degrade the superior creep and rupture properties of Ni‐based single crystal superalloys. Initially, small TCP phases are formed in the dendrite core during the early stages of the manufacturing process, such as solution heat treatment, and surrounded by a gamma prime (γ′) phase. Then, TCP phases continue to develop during full heat treatment. However, an additional heat treatment induces diffusion of refractory metals from the TCP phases into the γ′ phase and consequently, the TCP phases clearly disappear. After dissolution, the regions where the TCP phases existed are altered to a normal microstructure composed of γ channels and a normal cubic γ′ phase. Based on the observation result, the mechanism of the dissolution of TCP phases is discussed.