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1,234 result(s) for "Urban W."
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Water accelerated self-healing of hydrophobic copolymers
Previous studies have shown that copolymer compositions can significantly impact self-healing properties. This was accomplished by enhancement of van der Waals (vdW) forces which facilitate self-healing in relatively narrow copolymer compositional range. In this work we report the acceleration of self-healing in alternating/random hydrophobic acrylic-based copolymers in the presence of confined water molecules. Under these conditions competing vdW interactions do not allow H 2 O-diester H-bonding, thus forcing nBA side groups to adapt L-shape conformations, generating stronger dipole-dipole interactions resulting in shorter inter-chain distances compared to ‘key-and-lock’ associations without water. The perturbation of vdW forces upon mechanical damage in the presence of controllable amount of confined water is energetically unfavorable leading the enhancement of self-healing efficiency of hydrophobic copolymers by a factor of three. The concept may be applicable to other self-healing mechanisms involving reversible covalent bonding, supramolecular chemistry, or polymers with phase-separated morphologies. Self-healing of polymers became a vivid research area, but self-healing under water and its mechanistic concepts are less investigated. Here, the authors report water accelerated self-healing in a pMMA/nBA copolymer and demonstrate that perturbation of ubiquitous van der Walls forces upon mechanical damage in hydrophobic polymers in the presence of water is energetically unfavorable and accelerates self-healing.
Entropy and interfacial energy driven self-healable polymers
Although significant advances have been achieved in dynamic reversible covalent and non-covalent bonding chemistries for self-healing polymers, an ultimate goal is to create high strength and stiffness commodity materials capable of repair without intervention under ambient conditions. Here we report the development of mechanically robust thermoplastic polyurethane fibers and films capable of autonomous self-healing under ambient conditions. Two mechanisms of self-healing are identified: viscoelastic shape memory (VESM) driven by conformational entropic energy stored during mechanical damage, and surface energy/tension that drives the reduction of newly generated surface areas created upon damage by shallowing and widening wounds until healed. The type of self-healing mechanism is molecular weight dependent. To the best of our knowledge these materials represent the strongest ( S f  = 21 mN/tex, or σ f  ≈ 22 MPa) and stiffest ( J  = 300 mN/tex, or E  ≈ 320 MPa) self-healing polymers able to repair under typical ambient conditions without intervention. Since two autonomous self-healing mechanisms result from viscoelastic behavior not specific to a particular polymer chemistry, they may serve as general approaches to design of other self-repairing commodity polymers. Different self-healing materials were developed in the past but development of mechanically robust and affordable self-healing materials with high strain and stiffness is challenging. Here the authors develop mechanically robust thermoplastic polyurethane fibers and films capable of autonomous self-healing under ambient conditions.
Key-and-lock commodity self-healing copolymers
Biology provides many routes for self-healing or repair, but this trait is hard to endow into engineering materials. Although self-repair has been demonstrated for some polymers, it usually required specialized monomers. Urban et al. demonstrate that for a very narrow range of compositions, simple vinyl polymers based on methyl methacrylate and n -butyl acrylate show repeatable self-healing properties (see the Perspective by Sumerlin). A key characteristic of this system is that it relies on van der Waals interactions rather than the reformation of hydrogen or covalent bonds for repair. Science , this issue p. 220 ; see also p. 150 Commodity monomers are combined via a simple and scalable copolymerization to form self-healing polymers. Self-healing materials are notable for their ability to recover from physical or chemical damage. We report that commodity copolymers, such as poly(methyl methacrylate)/n-butyl acrylate [p(MMA/nBA)] and their derivatives, can self-heal upon mechanical damage. This behavior occurs in a narrow compositional range for copolymer topologies that are preferentially alternating with a random component (alternating/random) and is attributed to favorable interchain van der Waals forces forming key-and-lock interchain junctions. The use of van der Waals forces instead of supramolecular or covalent rebonding or encapsulated reactants eliminates chemical and physical alterations and enables multiple recovery upon mechanical damage without external intervention. Unlike other self-healing approaches, perturbation of ubiquitous van der Waals forces upon mechanical damage is energetically unfavorable for interdigitated alternating/random copolymer motifs that facilitate self-healing under ambient conditions.
Studying Atomic Structures by Aberration-Corrected Transmission Electron Microscopy
Seventy-five years after its invention, transmission electron microscopy has taken a great step forward with the introduction of aberration-corrected electron optics. An entirely new generation of instruments enables studies in condensed-matter physics and materials science to be performed at atomic-scale resolution. These new possibilities are meeting the growing demand of nanosciences and nanotechnology for the atomic-scale characterization of materials, nanosynthesized products and devices, and the validation of expected functions. Equipped with electron-energy filters and electron-energy-loss spectrometers, the new instruments allow studies not only of structure but also of elemental composition and chemical bonding. The energy resolution is about 100 milli-electron volts, and the accuracy of spatial measurements has reached a few picometers. However, understanding the results is generally not straightforward and only possible with extensive quantum-mechanical computer calculations.
Self-Repairing Oxetane-Substituted Chitosan Polyurethane Networks
Polyurethanes have many properties that qualify them as high-performance polymeric materials, but they still suffer from mechanical damage. We report the development of polyurethane networks that exhibit self-repairing characteristics upon exposure to ultraviolet light. The network consists of an oxetane-substituted chitosan precursor incorporated into a two-component polyurethane. Upon mechanical damage of the network, four-member oxetane rings open to create two reactive ends. When exposed to ultraviolet light, chitosan chain scission occurs, which forms crosslinks with the reactive oxetane ends, thus repairing the network. These materials are capable of repairing themselves in less than an hour and can be used in many coatings applications, ranging from transportation to packaging or fashion and biomedical industries.
Smell and taste dysfunction in patients with COVID-19
The plural of an anecdote is not evidence, yet anecdotal international reports are accumulating from ear, nose, and throat (ENT) surgeons and other health-care workers on the front lines that anosmia, with or without dysgeusia, are symptoms frequently associated with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection. To further complicate matters, immediate self-recognition of olfactory dysfunction is typically only present in the most severe cases, or it is only self-identified after a prolonged latency period.1,2 A scarcity of acute-phase advanced neuroimaging studies, difficulties in obtaining histopathological tissue specimens, and an absence of viral cultures of infected olfactory neuroepithelium compound the difficulties in studying this phenomenon. [...]in the context of normal trans-nasal airflow of odorant molecules (ie, no oedema in the nasal vault or olfactory cleft), and in the absence of intranasal disease (eg, infectious rhinosinusitis, allergic or vasomotor rhinitis, or polyposis), until now patients with sensorineural viral anosmia have been seldom seen in general otolaryngology practice—on the order of approximately one to two new-onset patients each year. [...]up until the coronavirus disease 2019 (COVID-19) pandemic, the low prevalence of sensorineural viral anosmia in society as a whole has made clinical research challenging.
Self‐Healable Fluorinated Copolymers Governed by Dipolar Interactions
Although dipolar forces between copolymer chains are relatively weak, they result in ubiquitous inter‐ and/or intramolecular interactions which are particularly critical in achieving the mechanical integrity of polymeric materials. In this study, a route is developed to obtain self‐healable properties in thermoplastic copolymers that rely on noncovalent dipolar interactions present in essentially all macromolecules and particularly fluorine‐containing copolymers. The combination of dipolar interactions between C─F and C═O bonds as well as CH2/CH3 entities facilitates self‐healing without external intervention. The presence of dipole‐dipole, dipole‐induced dipole, and induced‐dipole induced dipole interactions leads to a viscoelastic response that controls macroscopic autonomous multicycle self‐healing of fluorinated copolymers under ambient conditions. Energetically favorable dipolar forces attributed to monomer sequence and monomer molar ratios induces desirable copolymer tacticities, enabling entropic energy recovery stored during mechanical damage. The use of dipolar forces instead of chemical or physical modifications not only eliminates additional alternations enabling multiple damage‐repair cycles but also provides further opportunity for designing self‐healable commodity thermoplastics. These materials may offer numerous applications, ranging from the use in electronics, ion batteries, H2 fuel dispense hoses to self‐healable pet toys, packaging, paints and coatings, and many others. Fluorine‐containing acrylic‐based copolymers that rely on noncovalent dipolar interactions between CH2/CH3 entities as well as C─F and C═O bonds result in a viscoelastic response leading to macroscopic autonomous self‐healing. The presence of favorable dipolar forces is attributed to monomer sequences and monomer molar ratios facilitating desirable copolymer tacticity, enabling entropic energy storage, and recovery during multiple damage‐repair cycles.
Self-healing polymers
Self-healing is the capability of a material to recover from physical damage. Both physical and chemical approaches have been used to construct self-healing polymers. These include diffusion and flow, shape-memory effects, heterogeneous self-healing systems, covalent-bond reformation and reshuffling, dynamics of supramolecular chemistry or combinations thereof. In this Review, we discuss the similarities and differences between approaches to achieve self-healing in synthetic polymers, where possible placing this discussion in the context of biological systems. In particular, we highlight the role of thermal transitions, network heterogeneities, localized chemical reactions enabling the reconstruction of damage and physical reshuffling. We also discuss energetic and length-scale considerations, as well as scientific and technological challenges and opportunities. Self-healable polymers are materials that recover after physical damage. In this Review, we discuss the physical and chemical approaches to make self-healing polymers, with a focus on similarities with biological systems.
Direct Observation of Continuous Electric Dipole Rotation in Flux-Closure Domains in Ferroelectric Pb(Zr,Ti)O3
Nanometer-sized domains of ferroelectric materials have been considered for use in future nonvolatile memory devices. However, at these sizes the materials can spontaneously depolarize. Indirect evidence has suggested that a flux-closure domain structure could inhibit the spontaneous depolarization. Using aberration-corrected transmission electron microscopy, Jia et al. (p. 1420) were able to observe the continuous and gradual rotation of the dipoles to form a closed-domain structure directly. Low-dimensional ferroelectric structures are a promising basis for the next generation of ultrahigh-density nonvolatile memory devices. Depolarization fields, created by incompletely compensated charges at the surfaces and interfaces, depress the polarization of such structures. Theory suggests that under conditions of uncompensated surface charges, local dipoles can organize in flux-closure structures in thin films and vortex structures in nano-sized ferroelectrics, reducing depolarization fields. However, the continuous rotation of the dipoles required in vortex structures and the behavior of unit cell dipoles in flux-closure structures have never been experimentally established. By aberration-corrected transmission electron microscopy, we obtained experimental evidence for continuous rotation of the dipoles closing the flux of 180° domains in a ferroelectric perovskite thin film. [PUBLICATION ABSTRACT]
The effects of extremely wet planting conditions on maize and soybean yields
Short durations of very high spring soil moisture can influence crop yields in many ways, including delaying planting and damaging young crops. The central United States has seen a significant upward trend in the frequency and intensity of extreme precipitation in the 20th century, potentially leading to more frequent occurrences of saturated or nearly saturated fields during the planting season, yet the impacts of these changes on crop yields are not known. Here we investigate the yield response to excess spring moisture for both maize and soybean in the U.S. states of Illinois, Iowa, and Indiana, and the impacts of historical trends for 1950–2011. We find that simple measures of extreme spring soil moisture, derived from fine-scale daily moisture data from the Variable Infiltration Capacity (VIC) hydrologic model, lead to significant improvements in statistical models of yields for both crops. Individual counties experience up to 10 % loss in years with extremely wet springs. However, losses due to historical trends in excess spring moisture measures have generally been small, with 1–3 % yield loss over the 62 year study period.