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At least 397 records · Page 22

Nanostructure Scaling in Semi-Dilute Triblock Copolymer Gels

Here, there is a considerable body of work that describes the scaling of diblock copolymer micelle dimensions in dilute and semi-dilute solution based upon block degrees of polymerization and copolymer concentration. However, there is a lack of analogous information for semi-dilute ABA triblock copolymer gels, which consist of ABA triblock copolymer dissolved in midblock-selective (B-selective) solvent. The present study uses small angle X-ray scattering to extract micelle dimensions for numerous triblock copolymer gels that vary in copolymer identity (and hence block lengths) and copolymer concentration, as well as gels that contain various ratios of two unique triblock copolymers. Analysis of micelle structural data subsequently translates to universal scaling expressions for the micelle core radius – r A ≈ N A 0.53 N B -0.14 $\phi$ ABA 0.16 where N A and N B are the endblock and midblock degrees of polymerization, respectively, and $\phi$ ABA is the volume fraction of triblock copolymer in the gel – and for the intermicelle spacing – l AA ≈ N A 0.09 N B 0.29 $\phi$ ABA -0.35 . Each scaling expression describes the full collection of experimental data very well. Additionally, these scaling expressions are partially in line with expectations from semi-dilute diblock copolymer solution theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying the cooperative evolution of microphase segregation and nanostructural order in annealed polyurethanes of MDI-BDO-PTHF

Here, we quantify the relationship between microphase segregation and local structure development in thermoplastic polyurethanes. Samples were prepared with varying ratios of 4,40 -methylene diphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) to polytetrahydrofuran (PTHF) and annealed at temperatures T a between RT–140 °C for 20 h each. Distinct populations of smaller and larger ordered domains are distinguished by pair distribution func tion analysis. The intermediate-range order of nanoscale hard domains in the paracrystalline state (form I) is directly extracted and characterized. The results suggest that form I of the MDI-BDO:PTHF system presents a conformational and packing order similar to the form III structure, typically obtained from stretching/annealing, but with limited spatial coherence of 3–7 nm. Heating above T g of the hard segments is necessary to achieve a substantial structural response from the annealing treatment. Increasing T a promotes purification of the soft phase via microphase segregation, coalescence of the hard blocks, and growth of paracrystalline phase, while a minority fraction of longer-range ordered domains left over from production remains relatively constant. We observe a composition-dependent decrease in the average nearest-neighbor dis tance that can be correlated with the greater number of C C, C N, and C O bonds with increased hard segment content. A non-linear deviation in the trend is observed to correlate with sample densification. The mechanical and thermal behavior of the samples is intimately tied to the segregation state.

processing-structure-properties↗

Non-Equilibrium Synthesis of Highly Active Nanostructured, Oxygen-Incorporated Amorphous Molybdenum Sulfide HER Electrocatalyst

Molybdenum sulfide emerged as promising hydrogen evolution reaction (HER) electrocatalyst thanks to its high intrinsic activity, however its limited active sites exposure and low conductivity hamper its performance. To address these drawbacks, the non-equilibrium nature of pulsed laser deposition (PLD) is exploited to synthesize self-supported hierarchical nanoarchitectures by gas phase nucleation and sequential attachment of defective molybdenum sulfide clusters. Furthermore, the physics of the process are studied by in situ diagnostics and correlated to the properties of the resulting electrocatalyst. The as-synthesized architectures have a disordered nanocrystalline structure, with nanodomains of bent, defective S-Mo-S layers embedded in an amorphous matrix, with excess sulfur and segregated molybdenum particles. Oxygen incorporation in this structure fosters the creation of amorphous oxide/oxysulfide nanophases with high electrical conductivity, enabling fast electron transfer to the active sites. The combined effect of the nanocrystalline pristine structure and the surface oxidation enhances the performance leading to small overpotentials, very fast kinetics (35.1 mV dec -1 Tafel slope) and remarkable long-term stability for continuous operation up to -1 A cm -2 . This work shows possible new avenues in catalytic design arising from a non-equilibrium technique as PLD and the importance of structural and chemical control to improve the HER performance of MoS-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanostructured Conductive Metal Organic Frameworks for Sustainable Low Charge Overpotentials in Li–Air Batteries

Lithium-oxygen batteries are among the most attractive alternatives for future electrified transportation. However, their practical application is hindered by many obstacles. Due to the insulating nature of Li 2 O 2 product and the slow kinetics of reactions, attaining sustainable low charge overpotentials at high rates becomes a challenge resulting in the battery's early failure and low round trip efficiency. Herein, outstanding characteristics are discovered of a conductive metal organic framework (c-MOF) that promotes the growth of nanocrystalline Li 2 O 2 with amorphous regions. This provides a platform for the continuous growth of Li 2 O 2 units away from framework, enabling a fast discharge at high current rates. Moreover, the Li 2 O 2 structure works in synergy with the redox mediator (RM). The conductivity of the amorphous regions of the Li 2 O 2 allows the RM to act directly on the Li 2 O 2 surface instead of catalyst edges and then transport through the electrolyte to the Li 2 O 2 surface. This direct charge transfer enables a small charge potential of <3.7 V under high current densities (1-2 A g -1 ) sustained for a long cycle life (100-300 cycles) for large capacities (1000-2000 mAh g -1 ). These results open a new direction for utilizing c-MOFs towards advanced energy storage systems.

25 ENERGY STORAGE↗

Electrochemically Dealloyed 3D Porous Copper Nanostructure as Anode Current Collector of Li-Metal Batteries

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAh cm -2 and under a high current density of 10 mA cm -2 . This electrochemical fabrication method is facile and scalable for mass production. In conclusion, results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

36 MATERIALS SCIENCE↗

Electronic Melting of Silicon in Nanostructures using X-ray Forbidden Bragg Reflections

Abstract We carried out a short beamtime at the Pohang Accelerator Laboratory x-ray Free Electron Laser to perform a pump-probe (PP) laser excitation diffraction experiment on the silicon (222) forbidden Bragg peak. To limit the x-ray penetration, we used a “device layer” silicon film wafer bonded to a silicon substrate. The sample, specially fabricated by MEMC Electronic Materials, had a Si(100) substrate bonded to a 170 nm Si(100) film rotated at 45° for crystallographic isolation. A second sample was reactive-ion-etched down to 52 nm thickness. In the silicon lattice, the covalent bonds are seen exclusively at the 222 reflection. Upon laser excitation, these electrons are expected to be excited to the valence band on femtosecond electronic time scales. The Si(222) reflection is therefore expected to be extinguished on this fast time scale, while the electron–phonon coupled acoustic response is determined by the lattice dynamics. The latter is determined by the speed of sound over the device thickness, which is in the mid-picosecond range.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A novel battery scheme: Coupling nanostructured phosphorus anodes with lithium sulfide cathodes

Lithium-ion batteries are approaching their theoretical limit and can no longer keep up with the increasing demands of human society. Lithium-sulfur batteries, with a high theoretical specific energy, are promising candidates for next generation energy storage. However, the use of Li metal in Li-S batteries compromises both safety and performance, enabling dendrite formation and causing fast capacity degradation. Previous studies have probed alternative battery systems to replace the metallic Li in Li-S system, such as a Si/Li2S couple, with limited success in performance. Recently, there is a focus on red P as a favorable anode material to host Li. In this work, we establish a novel battery scheme by utilizing a P/C nanocomposite anode and pairing it with a Li 2 S coated carbon nanofiber cathode. We find that red P anode can be compatible in ether-based electrolyte systems and can be successfully coupled to a Li 2 S cathode. Our proof of concept full-cell displays remarkable specific capacity, rate and cycling performances. We expect our work will provide a useful alternative system and valuable insight in the quest for next generation energy storage devices.

25 ENERGY STORAGE↗

Intermetallic particle heterogeneity controls shear localization in high-strength nanostructured Al alloys

The mechanical behavior of two nanocrystalline Al alloys, Al-Mg-Y and Al-Fe-Y, is investigated with in-situ micropillar compression testing. Both alloys were strengthened by a hierarchical microstructure including grain boundary segregation, nanometer-thick amorphous complexions, carbide nanorod precipitates with sizes of a few nanometers, and submicron-scale intermetallic particles. The maximum yield strength of the Al-Mg-Y system is measured to be 950 MPa, exceeding that of the Al-Fe-Y system (680 MPa), primarily due to a combination of more carbide nanorods and more amorphous complexions. Both alloys exhibited yield strengths much higher than those of commercial Al alloys, and therefore have great potential for structural applications. However, some micropillar specimens were observed to plastically soften through shear banding. Post-mortem investigation revealed that intermetallic-free deformation pathways of a few micrometers in length were responsible for this failure. Further characterization showed significant grain growth within the shear band. The coarsened grains maintained the same orientation with each other, pointing to grain boundary mechanisms for plastic flow, specifically grain rotation and/or grain boundary migration. Here, the presence of intermetallic particles makes it difficult for both matrix and intermetallic grains to rotate into the same orientation due to the different lattice parameters and slip systems. Therefore, we are able to conclude that a uniform distribution of intermetallic particles with an average spacing less than the percolation length of shear localization can effectively prevent the maturation of shear bands, offering a design strategy for high-strength nanocrystalline Al alloys with both high strength and stable plastic flow.

36 MATERIALS SCIENCE↗

Ultra-high gamma irradiation of calcium silicate hydrates: Impact on mechanical properties, nanostructure, and atomic environments

The concrete biological shield in a nuclear power plant receives ~100–200 MGy gamma dosage during an 80-year design life. However, precise changes in the mechanical properties and atomic environments of C-S-H at ultrahigh irradiation dosages have not been systematically documented. Here, we report that irradiation decreases C-S-H basal spacing (~ 0.6 ± 0.1 Å for 189 MGy) and increases its Young's modulus, which is attributed to the lower basal spacing as the nano porosity potentially increased and microporosity remained unchanged. Irradiation also decreased the molecular water content and increased hydroxyl groups in C-S-H, showing that interlayer water removal reduces the basal spacing. Finally, 1 H and 29 Si NMR results indicate some disorder in the local proton CaO-H species and slight depolymerization of the silicate structure. Together, these results indicate that the C-S-H gel stiffens upon ultrahigh gamma irradiation dosage, a finding which concerns long-term nuclear power plants operations worldwide.

1H NMR↗