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1. Morphology and kinetics of asphalt binder microstructure at gas, liquid and solid interfaces

   https://doi.org/10.1111/jmi.12842  

   RAMM, A. ; DOWNER, M. C. ; SAKIB, N. ; BHASIN, A. ( November 2019 , Journal of Microscopy)

   We combined optical and atomic force microscopy to observe morphology and kinetics of microstructures (typically referred to as bees) that formed at free surfaces of unmodified Performance Graded (PG) 64‐22 asphalt binders upon cooling from 150°C to room temperature (RT) at 5°C min^–1, and changes in these microstructures when the surface was terminated with a transparent solid (glass) or liquid (glycerol) overlayer. The main findings are: (1) at free binder surfaces, wrinkled microstructures started to form near the crystallization temperature (∼45°C) of saturates such as wax observed by differential scanning calorimetry, then grew to ∼5 µm diameter, ∼25 nm wrinkle amplitude and 10–30% surface area coverage upon cooling to RT, where they persisted indefinitely without observable change in shape or density. (2) Glycerol coverage of the binder surface during cooling reduced wrinkled area and wrinkle amplitude three‐fold compared to free binder surfaces upon initial cooling to RT; continued glycerol coverage at RT eliminated most surface microstructures within ∼4 h. (3) No surface microstructures were observed to form at binder surfaces covered with glass. (4) Submicron bulk microstructures were observed by near‐infrared microscopy beneath the surfaces of all binder samples, with size, shape and density independent of surface coverage. No tendency of such structures to float to the top or sink to the bottom of mm‐thick samples was observed. (5) We attribute the dependence of surface wrinkling on surface coverage to variation in interface tension, based on a thin‐film continuum mechanics model.

   Asphalt binder, or bitumen, is the glue that holds aggregate particles together to form a road surface. It is derived from the heavy residue that remains after distilling gasoline, diesel and other lighter products out of crude oil. Nevertheless, bitumen varies widely in composition and mechanical properties. To avoid expensive road failures, bitumen must be processed after distillation so that its mechanical properties satisfy diverse climate and load requirements. International standards now guide these mechanical properties, but yield varying long‐term performance as local source composition and preparation methods vary.In situdiagnostic methods that can predict bitumen performance independently of processing history are therefore needed. The present work focuses on one promising diagnostic candidate: microscopic observation of internal bitumen structure. Past bitumen microscopy has revealed microstructures of widely varying composition, size, shape and density. A challenge is distinguishing bulk microstructures, which directly influence a binder's mechanical properties, from surface microstructures, which often dominate optical microscopy because of bitumen's opacity and scanning‐probe microscopy because of its inherent surface specificity. In previously published work, we used infrared microscopy to enhance visibility of bulk microstructure. Here, as a foil to this work, we use visible‐wavelength microscopy together with atomic‐force microscopy (AFM) specifically to isolatesurfacemicrostructure, to understand its distinct origin and morphology, and to demonstrate its unique sensitivity to surface alterations. To this end, optical microscopy complements AFM by enabling us to observe surface microstructures form at temperatures (50°C–70°C) at which bitumen's fluidity prevents AFM, and to observe surface microstructure beneath transparent, but chemically inert, liquid (glycerol) and solid (glass) overlayers, which alter surface tension compared to free surfaces. From this study, we learned, first, that, as bitumen cools, distinctly wrinkled surface microstructures form at the same temperature at which independent calorimetric studies showed crystallization in bitumen, causing it to release latent heat of crystallization. This shows that surface microstructures are likely precipitates of the crystallizable component(s). Second, a glycerol overlayer on the cooling bitumen results in smaller, less wrinkled, sparser microstructures, whereas a glass overlayer suppresses them altogether. In contrast, underlying smaller bulk microstructures are unaffected. This shows that surface tension is the driving force behind formation and wrinkling of surface precipitates. Taken together, the work advances our ability to diagnose bitumen samples noninvasively by clearly distinguishing surface from bulk microstructure.

    

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2. Accessibility and Mechanical Stability of Nanoporous Zinc Oxide and Aluminum Oxide Coatings Synthesized via Infiltration of Polymer Templates

   https://doi.org/10.3390/polym15204088  

   Omotosho, Khalil D. ; Lyon, Zachary ; Shevchenko, Elena V. ; Berman, Diana ( October 2023 , Polymers)

   The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlOx and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings—polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlOx and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlOx and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.

    

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3. Exploration of co-sputtered Ta 2 O 5 –ZrO 2 thin films for gravitational-wave detectors

   https://doi.org/10.1088/1361-6382/ac1b06  

   Abernathy, M ; Amato, A ; Ananyeva, A ; Angelova, S ; Baloukas, B ; Bassiri, R ; Billingsley, G ; Birney, R ; Cagnoli, G ; Canepa, M ; et al ( September 2021 , Classical and Quantum Gravity)

   Abstract We report on the development and extensive characterization of co-sputtered tantala–zirconia (Ta 2 O 5 -ZrO 2 ) thin films, with the goal to decrease coating Brownian noise in present and future gravitational-wave detectors. We tested a variety of sputtering processes of different energies and deposition rates, and we considered the effect of different values of cation ratio η = Zr/(Zr + Ta) and of post-deposition heat treatment temperature T a on the optical and mechanical properties of the films. Co-sputtered zirconia proved to be an efficient way to frustrate crystallization in tantala thin films, allowing for a substantial increase of the maximum annealing temperature and hence for a decrease of coating mechanical loss φ c . The lowest average coating loss was observed for an ion-beam sputtered sample with η = 0.485 ± 0.004 annealed at 800 °C, yielding φ ¯ c = 1.8 × 1 0 − 4 rad. All coating samples showed cracks after annealing. Although in principle our measurements are sensitive to such defects, we found no evidence that our results were affected. The issue could be solved, at least for ion-beam sputtered coatings, by decreasing heating and cooling rates down to 7 °C h −1 . While we observed as little optical absorption as in the coatings of current gravitational-wave interferometers (0.5 parts per million), further development will be needed to decrease light scattering and avoid the formation of defects upon annealing. 

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4. Solution-processed graphene films for electrochemical monitoring of extracellular nitric oxide released by breast cancer cells

   https://doi.org/10.1088/2053-1583/ad1251  

   Butler, Derrick ; Sankhe, Chinmay S. ; Khamsi, Pouya Soltan ; Gomez, Esther W. ; Ebrahimi, Aida ( December 2023 , 2D Materials)

   Nitric oxide (NO) plays an important role in cardiovascular function, immune response, and intercellular signaling. However, due to its short lifetime, real-time detection of NO is challenging. Herein, an electrochemical sensor based on fibronectin-modified, solution-processed graphene ink for NO detection is developed using a facile fabrication method involving spin-coating and hot-plate annealing. The sensor is first electrochemically characterized with a NO donor, spermine NONOate, exhibiting a dynamic range of 10–1000μM. The fibronectin-functionalized graphene supports the attachment and growth of MDA-MB-231 breast cancer cells, as confirmed by optical microscopy. Extracellular NO production is stimulated using the amino acid L-arginine. NO production results in morphological changes to the adhered cells, which are reversible upon the addition of the NO synthase antagonist Nω-nitro-L-arginine methyl ester. The production of NO is also confirmed using real-time amperometric measurements with the fibronectin-functionalized graphene sensors. While this work focuses on NO detection, this potentially scalable platform could be extended to other cell types with envisioned applications including the high-throughput evaluation of therapeutics and biocompatible coatings.

    

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5. In-vacuum measurements of optical scatter versus annealing temperature for amorphous Ta 2 O 5 and TiO 2 :Ta 2 O 5 thin films

   https://doi.org/10.1364/JOSAA.415665  

   Capote, Elenna M. ; Gleckl, Amy ; Guerrero, Jazlyn ; Rezac, Michael ; Wright, Robert ; Smith, Joshua R. ( March 2021 , Journal of the Optical Society of America A)

   Optical coatings formed from amorphous oxide thin films have many applications in precision measurements. The Advanced Laser Interferometer Gravitational-Wave Observatory (LIGO) and Advanced Virgo use coatings of$\mathrm{S}\mathrm{i}{\mathrm{O}}_2$(silica) and$\mathrm{T}\mathrm{i}{\mathrm{O}}_2:\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5$(titania-doped tantala) and post-deposition annealing to 500°C to achieve low thermal noise and low optical absorption. Optical scattering by these coatings is a key limit to the sensitivity of the detectors. This paper describes optical scattering measurements for single-layer, ion-beam-sputtered thin films on fused silica substrates: two samples of$\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5$and two of$\mathrm{T}\mathrm{i}{\mathrm{O}}_2:\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5$. Using an imaging scatterometer at a fixed scattering angle of 12.8°, in-situ changes in the optical scatter of each sample were assessed during post-deposition annealing to 500°C in vacuum. The scatter of three of the four coated optics was observed to decrease during the annealing process, by 25–30% for tantala and up to 74% for titania-doped tantala, while the scatter from the fourth sample held constant. Angle-resolved scatter measurements performed before and after vacuum annealing suggest some improvement in three of the four samples. These results demonstrate that post-deposition, high-temperature annealing of single-layer tantala and titania-doped tantala thin films in vacuum does not lead to an increase in scatter, and may actually improve their scatter.

    

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