Electrochemical Characterization and Microstructure Evolution of Ni-Rich Layered Cathode Materials by Niobium Coating/Substitution
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Enhancement of Conjugated Polymer Microstructure and Mixed-Conducting Properties via Chalcogenophene Heteroatom Substitution
Heteroatom substitution is a powerful tool to tune the intra- and intermolecular structure of conjugated polymers as well as their resulting optoelectronic and electrochemical properties. Here, a series of oligoethylene glycol bithiophene chalcogenophene polymers (p(g3T2-X)) with systematically varied furan, thiophene, selenophene, and tellurophene comonomers have been synthesized for mixed ionic-electronic conducting applications. Their microstructures have been thoroughly characterized ex situ and in situ with X-ray scattering, and their mixed conducting properties have been probed in electrochemical transistor testbeds. Chalcogenophene heteroatom choice was found to clearly dictate the polymer microstructure (crystallite dimensionality and orientation) and tune mixed conducting properties. Proceeding down Group 16, from O to Se systematically directed the molecular ordering of 2D polymer crystallites from face-on (O) to mixed (S) to edge-on (Se) orientations, with Te driving the polymer to form well-oriented edge-on 3D crystallites. Heteroatom dictated crystallite quality, and orientation tuned relative ionic transport by 2 orders of magnitude. Hole mobility (μ hole ) and mixed conducting figure of merit (μC*) were each tuned over an order of magnitude depending on heteroatom choice, with the Te-containing polymer reaching μ hole = 3.60 cm 2 V –1 s –1 and μC* = 483 F cm –1 V –1 s –1 , due to improved molecular ordering. Insights from this polymer series highlight target microstructures for enhanced mixed conduction in future conjugated polymers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure and properties of polymeric composite materials during 1501 days outer space exposure at Salyut-7 orbital station
Specimens of polymeric composite materials for aviation and space applications such as glass fiber reinforced plastics (GFRP), carbon fiber reinforced plastics (CFRP), organic fiber reinforced plastics (OFRP), and hybrid plastics (HP) based on epoxy compounds were exposed to the space environment on the surface of Salyut-7 orbital station. The space exposure lasted 1501 days as a maximum. The data relating to the change in mechanical properties, mass losses, glass transition temperature, linear thermal expansion coefficient, and microstructure after various periods of exposure are given. It has been found that the change in properties is caused by the processes of binder postcuring and microerosion of the exposed surface of plastics. The phenomenon of strengthening of the surface layer of hybrid composites, due to which the nature of destruction changes at bending loads, has been revealed.
Startsev, Oleg V.↗
Understanding Space Weathering of Carbonaceous Asteroids through H+ and He+ Ion Irradiation of the Murchison Meteorite
Airless planetary bodies are subject to space weathering processes such as micrometeoroid bombardment and solar wind irradiation. These processes alter the microstructural, chemical, and optical properties of planetary regoliths and, in turn, complicate interpretations of surface composition from remote sensing data and matching of meteorites to their parent bodies. Unlike lunar and ordinary chondrite materials, space weathering studies of primitive carbonaceous chondrites are still evolving [1]. Investigations that examine the spectral, microstructural, and chemical effects of space weathering on carbonaceous materials are critical for maximizing the scientific return of ongoing and future missions to C-complex asteroids, like the NASA OSIRIS-REx (Bennu) and JAXA Hayabusa2 (Ryugu) missions[2,3]. Here, we present results from our experimental simulation of solar wind weathering on organic-rich, C-complex asteroid surfaces in which we irradiated a slab of the Murchison CM2 chondrite with 1 keV/amu H+ and He+ ions.
D. L. Laczniak↗
Impact of grain boundaries on efficiency and stability of organic-inorganic trihalide perovskites
Organic-inorganic perovskite solar cells have attracted tremendous attention because of their remarkably high power conversion efficiencies. To further improve device performance, it is imperative to obtain fundamental understandings on the photo-response and long-term stability down to the microscopic level. Here, we report the quantitative nanoscale photoconductivity imaging on two methylammonium lead triiodide thin films with different efficiencies by light-stimulated microwave impedance microscopy. The microwave signals are largely uniform across grains and grain boundaries, suggesting that microstructures do not lead to strong spatial variations of the intrinsic photo-response. In contrast, the measured photoconductivity and lifetime are strongly affected by bulk properties such as the sample crystallinity. As visualized by the spatial evolution of local photoconductivity, the degradation process begins with the disintegration of grains rather than nucleation and propagation from visible boundaries between grains. In conclusion, our findings provide insights to improve the electro-optical properties of perovskite thin films towards large-scale commercialization.
14 SOLAR ENERGY↗
Materials aging at the mesoscale: Kinetics of thermal, stress, radiation activations
The complexity of materials aging may be seen as a result of the interplay between several activation processes operating on multiple spatial and temporal scales. Though the disciplines involved may seem disparate at first, material aging fundamentally could be linked by the same set of underlying activations and responses of the system. We view how recent studies of shear-induced deformation and rheological flow initiated in the soft-matter community can be leveraged to probe the mechanisms of radiation damage in nuclear materials. Bridging these two traditionally separate areas of research demonstrates the emerging notions of mesoscale science as a research frontier concerned with linking macroscale behavior to microscale processes in driven systems. We believe the combining of microstructure-sensitive measurements with fundamental theories and mechanism-specific simulations is crucial to addressing metastable materials responses of strongly activated states.
36 MATERIALS SCIENCE↗
Combinatorial Exploration and Mapping of Phase Transformation in a Ni–Ti–Co Thin Film Library
Combinatorial synthesis and high-throughput characterization of a Ni–Ti–Co thin film materials library are reported for exploration of reversible martensitic transformation. The library was prepared by magnetron co-sputtering, annealed in vacuum at 500 °C without atmospheric exposure, and evaluated for shape memory behavior as an indicator of transformation. Composition, structure, and transformation behavior of the 177 pads in the library were characterized using high-throughput wavelength dispersive spectroscopy (WDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and four-point probe temperature-dependent resistance (R(T)) measurements. A new, expanded composition space having phase transformation with low thermal hysteresis and Co > 10 at. % is found. Unsupervised machine learning methods of hierarchical clustering were employed to streamline data processing of the large XRD and XPS data sets. Through cluster analysis of XRD data, we identified and mapped the constituent structural phases. Finally, composition–structure–property maps for the ternary system are made to correlate the functional properties to the local microstructure and composition of the Ni–Ti–Co thin film library.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Characterization of Cotton Ball-like Au/ZnO Photocatalyst Synthesized in a Micro-Reactor
Noble metal/metal oxide nanostructures are an efficient system in photocatalysis. Continuous and scalable production of advanced particle systems will be a requirement for commercial-scale deployment for many applications, including photocatalysis. In this work, Au/ZnO structures were synthesized in a continuous flow micro-reactor at room temperature and the detailed characteristics of the product indicate a specific cotton ball-like core-shell microstructure that showcases specific advantages compared to traditional batch synthesis methods. The formation pathway of the core-shell Au/ZnO structures is discussed with the pH-dependent speciation diagram, and photocatalytic activity was assessed under simulated sunlight, demonstrating the enhanced performance of the cotton ball-like Au/ZnO microstructures in photocatalytic dye degradation. This work describes the application of microreaction technology in the continuous production of metal/metal oxide photocatalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A Semiconducting Two‐Dimensional Polymer as an Organic Electrochemical Transistor Active Layer
Abstract Organic electrochemical transistors (OECTs) are devices with broad potential in bioelectronic sensing, circuits, and neuromorphic hardware. Their unique properties arise from the use of organic mixed ionic/electronic conductors (OMIECs) as the active channel. Typical OMIECs are linear polymers, where defined and controlled microstructure/morphology, and reliable characterization of transport and charging can be elusive. Semiconducting two‐dimensional polymers (2DPs) present a new avenue in OMIEC materials development, enabling electronic transport along with precise control of well‐defined channels ideal for ion transport/intercalation. To this end, a recently reported 2DP, TIIP, is synthesized and patterned at 10 µm resolution as the channel of a transistor. The TIIP films demonstrate textured microstructure and show semiconducting properties with accessible oxidation states. Operating in an aqueous electrolyte, the 2DP‐OECT exhibits a device‐scale hole mobility of 0.05 cm 2 V –1 s –1 and a µ C * figure of merit of 1.75 F cm –1 V –1 s –1 . 2DP OMIECs thus offer new synthetic degrees of freedom to control OECT performance and may enable additional opportunities such as ion selectivity or improved stability through reduced morphological modulation during device operation.
2D-polymer↗
High efficient ZnO nanowalnuts photocatalyst: A case study
Highlights: • Walnut-like ZnO nanostructures are synthesized through a facile hydrothermal method. • Morphologies and microstructures of the as-obtained ZnO products were investigated. • The photocatalytic results demonstrate that methyl orange (MO) aqueous solution can be degraded over 97% after 45 min under UV light irradiation. - Abstract: Walnut-like ZnO nanostructures are successfully synthesized through a facile hydrothermal method. The structure and morphology of the as-synthesized products were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The photocatalytic properties of ZnO nanowalnuts are investigated by photodegradating several organic dyes, such as Congo red (CR), methyl orange (MO) and eosin red aqueous solutions under UV irradiation, respectively. The results demonstrate that methyl orange (MO) aqueous solution can be degraded over 97% after 45 min under UV light irradiation. In addition, eosin red and Congo red (CR) aqueous solution degradation experiments are also conducted in the same condition, respectively. It showed that ZnO nanowalnuts represent high photocatalytic activities with a degradation efficiency of 87% for CR with 115 min of irradiation and 97% for eosin red with 55 min of irradiation. The reported ZnO products may be promising candidates as the photocatalysts in waste water treatment.
36 MATERIALS SCIENCE↗
Oxidation behaviors of matrix-grade graphite during water vapor ingress accidents for high temperature gas-cooled reactors
Water ingress into cores of high temperature gas-cooled reactors (HTGRs) can cause serious safety problems in graphitic components, especially for matrix graphite, which is more vulnerable than nuclear graphite. Here in this study, oxidation behaviors of a matrix-grade graphite, ARB-B1, were investigated under simulated water ingress accidental conditions. The oxidation tests were conducted in water vapor/helium mixed atmospheres at elevated temperatures up to 1200 °C. Oxidation rates and activation energy were evaluated by mass loss measurements. The activation energy was 121.5 kJ/mol in the considered temperature range, indicating only one oxidation regime-in-pore diffusion assisted by cracks. The cracks originated from the fabrication process, acting as penetration paths for the oxidant, played an important role in the oxidation behaviors. Ungraphitized binder oxidation occurred at all temperatures, while apparent oxidation of filler particles started from 1100 °C. Moreover, oxidation effects on compressive properties and hardness of the matrix graphite were discussed in terms of oxidized microstructures. This first detailed study on matrix graphite oxidation in water vapor provides important kinetics knowledge and microstructural and mechanical data for accidental scenarios of HTGRs as well as for development of new matrix graphite materials.
36 MATERIALS SCIENCE↗
Simulating Charge, Spin, and Orbital Ordering: Application to Jahn–Teller Distortions in Layered Transition-Metal Oxides
The degrees of freedom associated with orbital, spin, and charge ordering can signifcantly affect the properties of many crystalline solids, including battery materials, high-temperature superconductors, and naturally occurring minerals. Our research reports on the development of a computational framework to systematically explore the ordering of electronic degrees of freedom and presents results on orbital ordering associated with Jahn–Teller distortions in four layered oxides relevant for Li- and Na-ion batteries: LiNiO 2 , NaNiO 2 , LiMnO 2 , and NaMnO 2 . Our calculations reveal a criterion for the stability of orbital orderings in these layered materials: each oxygen atom must participate in two short and one long transition-metal/oxygen bond. The only orderings that satisfy this stability criterion are row orderings, such as the “zigzag” ordering. The near degeneracy of such row-orderings in LiNiO 2 suggests that boundaries between domains with distinct but symmetrically equivalent Jahn–Teller distortions will be relatively low in energy. Based on this finding, we speculate that a microstructure consisting of nanoscale Jahn–Teller domains could be responsible for the apparent absence of a collective distortion in experiments on LiNiO 2 .
25 ENERGY STORAGE↗
Kinetics and Mechanism of Nickel Oxide Reduction by Methane
Nickel oxide reduction by methane is of particular importance in catalysis, extractive metallurgy, and clean power generation technologies. Despite extensive investigations of the NiO + CH 4 reaction, many questions remain about its kinetics and molecular and structural transformation mechanisms. We discuss the reduction kinetics of bulk polycrystalline NiO by CH 4 using a new calorimetric method. The technique permits rapid, controllable heating of the NiO/Ni wires and continuous data (electrical power, the electrical resistivity of the wire, and temperature) acquisition with a frequency of 10 kHz. The method also allows arresting and preservation of the structure of the sample by programmed termination of electric power in thin specimens. This approach, coupled with ex situ electron microscopy, allows determination of the reaction rate and tracking of the ongoing structural transformations. The mechanism of NiO reduction by methane is suggested based on direct correlations between reaction kinetics and the observed microstructure transformations. The kinetic data treatment revealed that the nucleation-growth model describes the reaction kinetics. Ex situ microscopy observations of reacted specimens showed that the first nuclei rapidly accelerate the process. Pore formation occurs at the nucleation sites, and the porous structure then quickly grows into the bulk NiO. The second type of reduced Ni microstructure, compact layer, can be observed only on the outer surface of the wire. Based on kinetic data and microstructural observations, a mechanism of reduction was suggested according to which porous microstructure forms predominantly by NiO reduction with carbon. The compact layer observed on the outer surface of the wire forms through the diffusion-controlled hydrogen reduction.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Carbonylative Co- and Terpolymerizations of 10-Undecen-1-ol: A Route to Polyketoesters with Tunable Compositions
A strategy to synthesize branched polyketoesters from the carbonylative polymerization of bifunctional α,ω-alkenols such as 10-undecen-1-ol is presented. This strategy hinges on the competitive application of two related catalytic manifolds, alternating alkene/CO copolymerization, and alkene hydroesterification, which share a common metal acyl intermediate. Small molecule model studies of cationic Pd-catalyzed alkene carbonylation in the presence of alcohols demonstrate that the relative rates of ketone formation (through alternating alkene/CO insertion) and ester formation (through metal acyl alcoholysis) can be tuned across a wide range through judicious bis(phosphine) ligand design. Carbonylative polymerization of 10-undecen-1-ol with a (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 catalyst (dppp(3,5-CF 3 ) 4 = 1,3-bis[bis[3,5-bis(trifluoromethyl)phenyl]-phosphino]propane) led to the formation of high molecular weight polyketoesters with intermediate dispersity (M n > 20,000 g/mol, D- = 2.6) and a ketone/ester microstructure ratio of approximately 1:2. In these polymerization reactions, deploying electron-deficient bis(phosphines) to suppress deleterious alkene isomerization was the key to accessing the high molecular weight polymer. Further, terpolymerization reactions of 1-hexene/10-undecen-1-ol/CO or 1-fluoro-10-undecene/10-undecen-1-ol/CO by (dppp(3,5-CF 3 ) 4 )Pd(OTs) 2 were also successful. Furthermore, this proof of concept polymerization unlocks access to tunable polymer microstructures without extensive postpolymerization treatment.
10-undecen-1-ol↗
New donor polymer with tetrafluorinated blocks for enhanced performance in perylenediimide-based solar cells
The synthesis of a new tetrafluorinated semiconducting donor polymer, poly[(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophene-2-yl)-benzo[1,2-b:4,5-b']dithiophene)-alt-(5,6-difluoro-4,7-(4-(2-ethylhexyl)-dithien-2-yl-2,1,3-benzothiadiazole)] (PBTZF4), and its photovoltaic performance in bulk heterojunction (BHJ) blends with the non-fullerene molecular acceptor [1,2:3,4]-bis-[N,N'-bis-1-pentylhexyl-perylenediimide-1,12-yl]-benzene (bPDI2P), are reported. PBTZF4:bPDI2P solar cells exhibit a high open circuit voltage (V oc ) of 1.118 V, a short circuit current density (J sc ) of 10.02 mA cm –2 , and a fill factor (FF) of 49.5%, affording a power conversion efficiency (PCE) of 5.55%. Interestingly, a lower PCE of 3.68% is obtained with the difluorinated analogue, poly[(4,8-bis(5-(2-ethylhexyl)-thiophene-2-yl)-benzo[1,2-b:4,5-b']dithiophene)- alt -(5,6-difluoro-4,7-(4-(2-ethyl-hexyl)-dithien-2-yl-2,1,3-benzothiadiazole)] (PBTZF2). Both PBTZF4:bPDI2P and PBTZF2:bPDI2P cells benefit from complementary (donor/acceptor) light absorption and very low geminate recombination, with bimolecular recombination being the dominant loss mechanism, as established by femtosecond transient absorption spectroscopy. DFT computation and physicochemical characterization data argue that the “additional” tetrafluorination planarizes the PBTZF4 backbone and enhances aggregation versus PBTZF2, affording superior charge carrier transport as assayed by field-effect mobility. In addition, fluorine-originated HOMO stabilization, –5.41 eV for PBTZF4 versus –5.33 eV for PBTZF2, and a superior blend microstructure afford a higher PBTZF4:bPDI2P solar cell PCE versus PBTZF2:bPDI2P.
36 MATERIALS SCIENCE↗
Examination of the α-ω two-phase shock-induced microstructure in zirconium and titanium
Omega (ω) phase is formed in alpha (α) zirconium during dynamic loading and can be retained in the recovered material. The pathway for the α to ω change (or the reverse transformation) is not well understood. Zirconium was shock-loaded and the resulting two-phase microstructure was examined. Electron backscatter diffraction (EBSD) was used to characterize the orientation relationships and habit planes between phases to understand the pathways between α and ω phases and compare to Molecular Dynamics (MD) simulations. Based on key microstructural features, a significant amount of α phase appears to have originated from the reverse transformation from ω-Zr on unloading. Results of microstructural analysis will be discussed, along with implications toward phase transformation pathways.
36 MATERIALS SCIENCE↗
A compliant, high failure strain, fibre-reinforced glass-matrix composite
A glass-matrix composite reinforced by discontinuous graphite fibers was produced by hot pressing glass-powder-impregnated two-dimensional arrays of in-plane randomly oriented graphite fibers held together by approximately 5-10% by weight of organic binder (generally polyester). The composite tensile behavior is characterized by a highly nonlinear stress-strain curve which differs markedly from that of either unreinforced glass or a similarly reinforced epoxy-matrix composite. By virtue of this nonlinearity, the composite is able to redistribute applied stresses to achieve a high load-carrying capacity. The fibrous microstructure and the low fiber-matrix bond provide a mechanism for achieving high fracture toughness and unusually high compliance. For a 96%-silica-matrix composite, the strength is retained to over 1000 C.
Prewo, K. M.↗