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At least 1,693 records · Page 94

Utilizing a Dynamic Segmentation Convolutional Neural Network for Microstructure Analysis of Additively Manufactured Superalloy 718

Additive manufacturing (AM) is revolutionizing almost all industries through the production of intricate geometries previously prohibited by cost or machinability. Ni-based superalloys form a primary alloy class for high temperature applications in the petrochemical, aerospace, and nuclear industries because of their intrinsic resistance to creep and the ability to heat treat the superalloy for high strength. Despite these attractive properties, the extreme work hardening of Ni-based superalloys makes traditional manufacturing of complex shapes difficult and thus, these alloys are an attractive target for AM. Superalloy 718 was chosen as an example superalloy because of the wide variety of precipitates that can form within its composition space from the repetitive heating and cooling cycles of the AM process. The precipitates and other microstructure features, such as grain boundaries and dislocations, will dictate the mechanical properties and thus, there is an extensive challenge to characterize the size, number density, composition, and volume fraction of each microstructural feature from AM fabrication using analytical electron microscopy. This work focused on the application of a pixel-wise classification machine learning (ML) model called a dynamic segmentation convolutional neural network (DSCNN) to identify the microstructural features of an as-fabricated additively manufactured superalloy 718.

Taller, Stephen↗

Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation

In this work, we have synthesized the products of fluoroethylene carbonate (FEC) and vinylene carbonate (VC) via lithium naphthalenide reduction. By analyzing the resulting solid precipitates and gas evolution, our results confirm that both FEC and VC decomposition products include HCO 2 Li, Li 2 C 2 O 4 , Li 2 CO 3 , and polymerized VC. For FEC, our experimental data supports a reduction mechanism where FEC reduces to form VC and LiF, followed by subsequent VC reduction. In the FEC reduction product, HCO 2 Li, Li 2 C 2 O 4 , and Li 2 CO 3 were found in smaller quantities than in the VC reduction product, with no additional fluorine environments being detected by solid-state nuclear magnetic resonance or X-ray photoelectron spectroscopy analysis. With these additives being practically used in higher (FEC) and lower (VC) concentrations in the base electrolytes of lithium-ion batteries, our results suggest that the different relative ratios of the inorganic and organic reduction products formed by their decomposition may be relevant to the chemical composition and morphology of the solid electrolyte interphase formed in their presence.

36 MATERIALS SCIENCE↗

GeI 2 Additive for High Optoelectronic Quality CsPbI 3 Quantum Dots and Their Application in Photovoltaic Devices

Trioctylphosphine (TOP)-based syntheses of CsPbI 3 perovskite quantum dots (QDs) yield unprecedented high photoluminescence quantum yield (PL QY), lower Stokes shifts, and longer carrier lifetimes due to their enhanced crystallinity. This synthetic route relies on a heavily Pb-rich condition or a large Pb:Cs molar ratio in precursor solution to produce QDs with appropriate stoichiometry as well as to guarantee a good colloidal stability. The high Pb condition is achieved by a high concentration of PbI 2 prepared in TOP. Here we find such Pb-rich strategies can be avoided by providing additional iodine ions using other metal halide salts. In particular GeI 2 , which contrary to PbI 2 , readily dissolves in TOP. CsPbI 3 QDs prepared using PbI 2 /GeI 2 combination show near-unity PL QY and improved chemical stability compared to the previous synthetic route. Furthermore, we find no sign of Ge incorporation in the QDs (compositionally or energetically). The ensuing QD solar cells deliver power conversion efficiency of 12.15% and retain 85% of its peak performance after storage over 90 days. The PbI 2 /GeI 2 dual-source iodine synthetic approach presented here represents a more rational and robust route to high-quality CsPbI 3 QDs. to guarantee a good colloidal stability. The high Pb condition is achieved by a high concentration of PbI2 prepared in TOP. Here we find such Pb-rich strategies can be avoided by providing additional iodine ions using other metal halide salts. In particular GeI 2 , which contrary to PbI 2 , readily dissolves in TOP. CsPbI 3 QDs prepared using PbI 2 /GeI 2 combination show near-unity PL QY and improved chemical stability compared to the previous synthetic route. Furthermore, we find no sign of Ge incorporation in the QDs (compositionally or energetically). The ensuing QD solar cells deliver power conversion efficiency of 12.15% and retain 85% of its peak performance after storage over 90 days. The PbI 2 /GeI 2 dual-source iodine synthetic approach presented here represents a more rational and robust route to high-quality CsPbI 3 QDs.

14 SOLAR ENERGY↗

ortho -Fluoro or ortho Effect? Oxidative Addition of Zerovalent Nickel into the C–CN Bond of Substituted Benzonitriles

Substitution effects on the oxidative addition of [Ni(dmpe)] to the C—CN bond of CF 3 and CH 3 substituted benzonitriles was studied by DFT and compared to their F analogs. C—CN oxidative addition products were stabilized slightly more by the first o-CF 3 group (-7.4 kcal/mol) compared to F groups (-6.6 kcal/mol per o-F), but due to steric crowding the second o-CF 3 group did not show considerably more stabilization (-0.8 kcal/mol). CH 3 groups led to destabilization.

02 PETROLEUM↗

Formation of 1 H -Phenalene (C 13 H 10 ) in the Taurus Molecular Cloud via Methylidyne Addition-Cyclization-Aromatization (MACA)

The formation of 1H-phenalene (C 13 H 10 ) in cold molecular clouds, such as the Taurus Molecular Cloud-1 (TMC-1), presents a significant challenge to traditional astrochemical models, which predominantly suggest high-temperature pathways for polycyclic aromatic hydrocarbon (PAH) formation. In this study, we explore computationally the Methylidyne Addition-Cyclization-Aromatization (MACA) mechanism as a viable, barrierless pathway for phenalene synthesis under low-temperature conditions. Through electronic structure calculations and Rice–Ramsperger–Kassel–Marcus (RRKM) statistical methods, we demonstrate that the reaction of 1-vinylnaphthalene (C 10 H 7 C 2 H 3 ) with the methylidyne radical (CH) leads to the formation of 1H-phenalene via a bimolecular reaction, a process that is exoergic and without entrance barrier. The MACA mechanism facilitates the growth of the aromatic carbon backbone via a [5 + 1] ring annulation, providing a new insight into PAH formation in cold molecular clouds. Notably, the MACA mechanism has previously been shown to form indene (C9H8), which was detected in TMC-1 as well, via a [4 + 1] annulation, demonstrating its potential to produce a variety of complex PAHs by addition of a five- and six-membered ring to a benzene moiety via [4 + 1] and [5 + 1] annulation, respectively. As a result, this work highlights the importance of barrierless, exoergic reactions involving MACA in the synthesis of complex aromatic molecules in space, expanding our physicochemical understanding of carbon-rich chemistry in cold molecular clouds.

Aromatic compounds↗

Reversible Olefin Addition to Extended Lattices of a Nickel–Selenium Framework

We performed density functional theory computations to study the structural and electronic properties as the basis of ethylene addition activity for [Ni(XC)4]n (X = Se, S)-extended lattices. We demonstrated that the mechanism of ethylene cycloaddition to a periodic [Ni(SeC)4]n two-dimensional (2D) network is analogous to that previously described for [Ni(SC)4]n 2D sheets and similar to the metal bis(dithiolene) molecular complexes [M(S2C2R2)2] (M = Ni, Pd, Pt, Co, Cu). These nanosheet materials avoid decomposition upon olefin addition, which is one of the main limitations of the molecular metal bis(dithiolene) complexes, as we find the decomposition processes to be thermodynamically unfavorable. Our calculations also suggest that the preferred conformation of the [Ni(SeC)4]n bilayer lattice is parallel displaced, with the Se atoms positioned above the Ni atoms, which is different from the eclipsed conformation found for [Ni(SC)4]n. We also managed to optimize an adduct of [Ni(SC)4]n in the bilayer form, which exceed the ethylene coverage of molecular complexes. We calculate that the preferred three-dimensional geometry of the stacked sheets is eclipsed because of strong van der Waals interactions. Such an arrangement of the sheets indicates that these materials should be highly porous, pointing to the high capacity for olefin bindings. Indeed, a few moderately stable ethylene adducts have been located. Owing to their unique structures and chemical reactivity, these newly predicted materials can be potentially developed as electrocatalysts for olefin purification. © 2018 American Chemical Society.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roll-to-Roll Scalable Production of Ordered Microdomains through Nonvolatile Additive Solvent Annealing of Block Copolymers

A new method, “nonvolatile solvent vapor annealing” (NVASA), has been developed to anneal block copolymers during film deposition by controlling the solvent drying process. Precise amounts of high boiling point additive added to the polymer solution briefly remain in the polymer film after casting, leaving the film in a swollen state, increasing its chain mobility, and ultimately improving domain order. We demonstrated the effectiveness of NVASA on several block copolymer systems and used in situ grazing incidence small-angle X-ray scattering (GISAXS) to validate the ordering process during the self-assembly. The simplicity and reproducibility of the method is attractive for implementation in large-scale manufacturing processes such as roll-to-roll printing as swell ratio is easily controlled by the amount of additive used and separate annealing steps are not needed. This work potentially introduces a new way to quickly and cost effectively anneal block copolymers.

36 MATERIALS SCIENCE↗

1,2-Addition of Formic or Oxalic Acid to – N{CH 2 CH 2 (PiPr 2 )} 2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid

(PN H P)Mn(CO) 2 (I) carboxylate complexes (PN H P = HN{CH 2 CH 2 (PiPr 2 )} 2 ) were prepared in this study via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO) 2 (PNP = the deprotonated, amide form of the ligand –N{CH 2 CH 2 (PiPr 2 )} 2 ). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H 2 , CO 2 , and H 2 O. Lastly, the addition of LiBF 4 exhibited a strong inhibitory effect on the catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved CO 2 Capture Performance of Electrochemically Mediated Amine Regeneration Processes with Ionic Surfactant Additives

For the effective reduction of global CO 2 emissions, it is essential to develop and deploy efficient and cost-effective technologies for CO 2 capture, especially from large point sources. We recently developed an electrochemically mediated amine regeneration (EMAR) system to replace traditional thermal desorption for the capture of CO 2 from post-combustion flue gases. Despite EMAR effectiveness on a laboratory scale, concerns regarding the high gas-to-liquid ratio in the electrochemical cell and long-term instability of the electrodes need to be addressed before further scale-up of the process to a pilot plant and beyond can be entertained. Accordingly, we investigated the effect of using sodium dodecyl sulfate (SDS) as an anionic surfactant and dodecyltrimethylammonium bromide (DTAB) as a cationic surfactant on the process operation. It was found that it is advantageous to use an anionic surfactant for a system such as EMAR that contains hydrophilic electrodes and a positively charged electrochemically active species. The overall cell resistance was notably reduced when SDS anionic surfactant was used. The precipitation of copper particles observed in the anode outlet when no surfactant was used was effectively avoided when SDS was added to the electrolyte, resulting in electrode stability. In addition, smaller gas bubbles were produced in the presence of the SDS surfactant, which resulted in less blockage of the electrode by the gas with a resultant lower cell potential under constant current conditions, driving more efficient CO 2 desorption. This led to an ~25% reduction in the electrochemical energy requirement, the lowest ever achieved experimentally for the EMAR process. Altogether, the addition of a very low concentration of SDS resulted in the successful circumvention of the important problems faced by the EMAR system regarding further scale-up.

36 MATERIALS SCIENCE↗

Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium–Sulfur Batteries

Lithium-sulfur (Li-S) batteries are promising owing to their high energy density, environmental benignity, and low cost. Most of the commonly used binders in Li-S battery cathodes are inert and have no significant effect on the challenges of sulfur as a cathode material, such as the polysulfide shuttle effect, low ionic/electronic conductivity, and a sluggish redox reaction. In this work, we demonstrate the use of poly(vinylferrocene) (PvFc) as a binder additive that can effectively increase the ionic conductivity of the cathode and act as a sulfide confining agent. Electrochemical tests performed with PvFc as part of the binder mixture used to cast the cathodes demonstrate an increase in rate capability and cycle life when compared to the baseline samples. Ionic conductivity measurements and X-ray photoelectron spectroscopy suggest that the π-cation molecular interaction between the cyclopentadienyl rings from ferrocene and Li + act like an ion couple with ferrocene acting as a static, covalently bound acceptor of Li + ions that enhances their mobility through the cathode. This coupled with the affinity between the ferrocenyl cations and the Li salt anions, which provides more distribution of counterions for Li + movement and improves accessibility to the cathode S reservoir, make PvFc a promising ionomer for Li-S batteries. In addition, the π-cation bonds between cyclopentadienyl and lithium polysulfides produce a sulfide confining effect that mitigates capacity fade through polysulfide dissolution. Furthermore, this work demonstrates an expansion in the utility of PvFc as a component in Li-ion batteries, which so far is mostly limited to use as an active material in organometallic batteries.

25 ENERGY STORAGE↗

Ammonium Additives to Dissolve Lithium Sulfide through Hydrogen Binding for High-Energy Lithium–Sulfur Batteries

In rechargeable Li-S batteries, the uncontrollable passivation of electrodes by highly insulating Li2S limits sulfur utilization, increases polarization and decreases cycling stability. Dissolving Li2S in organic electrolyte is a facile solution to maintain the active reaction interface between electrolyte and sulfur cathode, and thus address the above issues. Herein, ammonium salts are demonstrated as effective additives to promote the dissolution of Li2S to 1.25 M in DMSO solvent at room temperature. NMR measurements show that the strong hydrogen binding effect of N-H groups plays a critical role in dissolving Li2S by forming complex ligands with S2- anions coupled with the solvent’s solvating surrounding. Ammonium additives in electrolyte can also significantly improve the oxidation kinetics of Li2S, therefore enables the direct use of Li2S as cathode material in Li-S battery system in the future. This provides a new approach to manage the solubility of lithium sulfides through cation coordination with sulfide anion.

Environmental Molecular Sciences Laboratory↗

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2 -LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2 -LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.

25 ENERGY STORAGE↗

Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites

The addition of hard fillers to a polymer matrix is a well-known process for achieving mechanical reinforcement. With a decrease in the size of the fillers, the contribution from polymer–particle nanometer-sized interfaces become significant, and these interfaces affect the mechanical performance of polymer nanocomposites (PNCs) beyond the limits established for conventional composites. However, the molecular mechanisms underlying the improvement in the mechanical performance of glassy PNCs remain unresolved, necessitating a deeper understanding of the structure–property relationships in these intrinsically heterogeneous systems. In this effort, by using Brillouin light scattering (BLS) and dynamic mechanical analysis (DMA), we demonstrated that adding shorter chains to a PNC prepared with high molecular weight polymers significantly improved the mechanical properties of the PNC in the glassy state. The strongest enhancement of mechanical properties occurred at an optimum concentration of short chains. This is in contrast to behavior of the glass transition temperature of PNCs which shows a monotonic decrease with an increase in the concentration of shorter chains. Using experimental data and coarse-grained molecular dynamics (MD) simulations, we have identified the molecular mechanism leading to the observed non-monotonic changes in mechanical reinforcement. Here, this mechanism includes changes in the nanoscale organization at the interface, combined with chain stretching amplified by the addition of the short chains. Overall, our approach paves a simple, cost-effective pathway to fabricating glassy PNCs with significantly improved mechanical properties that will fill various practical needs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Block Polyelectrolyte Additives That Modulate the Viscoelasticity and Enhance the Printability of Gelatin Inks at Physiological Temperatures

We demonstrate the utility of block polyelectrolyte (bPE) additives to enhance viscosity and resolve challenges with the three-dimensional (3D) printability of extrusion-based biopolymer inks. The addition of oppositely charged bPEs to solutions of photocurable gelatin methacryloyl (GelMA) results in complexation-driven self-assembly of the bPEs, leading to GelMA/bPE inks that are printable at physiological temperatures, representing stark improvements over GelMA inks that suffer from low viscosity at 37 °C, leading to low printability and poor structural stability. The hierarchical microstructure of the self-assemblies (either jammed micelles or 3D networks) formed by the oppositely charged bPEs, confirmed by small-angle X-ray scattering, is attributed to the enhancements in the shear strength and printability of the GelMA/bPE inks. Varying bPE concentration in the inks is shown to enable tunability of the rheological properties to meet the criteria of pre- and postextrusion flow characteristics for 3D printing, including prominent yielding behavior, strong shear thinning, and rapid recovery upon flow cessation. Moreover, the bPE self-assemblies also contribute to the robustness of the photo-cross-linked hydrogels; photo-cross-linked GelMA/bPE hydrogels are shown to exhibit higher shear strength than photo-cross-linked GelMA hydrogels. Last, the assessment of the printability of GelMA/bPE inks indicates excellent printing performance, including minimal swelling postextrusion, satisfactory retention of the filament shape upon deposition, and satisfactory shape fidelity of the various printed constructs. We envision this study to serve as a practical guide for the printing of bespoke extrusion inks where bPEs are used as scaffolds and viscosity enhancers that can be emulated in a range of photocurable precursors.

36 MATERIALS SCIENCE↗

Additive-Induced Morphology Change of Polymer Film Enables Enhanced Charge Mobility and Faster Organic Electrochemical Transistor Switching

Conjugated polymers (CPs) play an important role in organic electrochemical transistors (OECTs) for bioelectronics and related applications, where they serve as channel materials. Currently, most successful polymers for CPs are re-engineered from traditional CPs by replacing hydrophobic alkyl side chains with hydrophilic ethylene glycol or ionic groups. Frustratingly, the enhanced ion transport often compromises the charge mobility of the original CP. In this work, we present an additive-mediated method to construct a modified poly(3-hexylthiophene) (P3HT) film to enable efficient ion migration. The additive is designed with a cleavable diazo group that releases nitrogen and 2-methoxyethanol, a volatile compound, to alter the P3HT film morphology. OECTs based on the film exhibit improved response times. Interestingly, the process also enhances the crystallinity of P3HT, leading to higher hole mobility compared with pristine P3HT. This study proposes an in situ strategy to achieve the functionality of the OMIEC via morphological regulation, offering a promising route to simultaneously enhance both ion accessibility and charge mobility.

Organic polymers↗

Additive-Free Ruthenium-Catalyzed Hydrogen Production from Aqueous Formaldehyde with High Efficiency and Selectivity

In this study, an efficient water-soluble ruthenium complex was developed for selective hydrogen production from aqueous formaldehyde under mild conditions with a high yield (~95%). Hydrogen production by this catalytic system proceeds without using any additives or organic solvents, leading to a high turnover frequency (8300 h –1 ) and a record turnover number of 24 000. Additionally, based on mechanistic experiments and density functional theory (DFT) calculations, a step-by-step mechanism has been proposed for the catalytic cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Simple Bond-Additivity Model Explains Large Decreases in Heats of Adsorption in Solvents Versus Gas Phase: A Case Study with Phenol on Pt(111) in Water

Previously, we reported the low-coverage heat of adsorption of phenol on Pt(111) facets of a Pt wire in aqueous phase to be approximately 21 kJ/mol (relative to aqueous phenol) on the basis of measurements of the adsorption equilibrium constant. This is much smaller than the heat we reported for gas-phase phenol adsorption at this same low coverage on single-crystal Pt(111) under ultrahigh vacuum (200 kJ/mol) on the basis of adsorption calorimetry measurements. Here we quantitatively analyze the individual contributions that give rise to this 179 kJ/mol difference using a simple pairwise bond-additivity model, taking advantage of experimental data from the literature to estimate the bond energies. The dominant contribution to the lowering in heat when phenol is adsorbed in water is the energy cost to break the strong bond of liquid water to Pt(111) (~116 kJ per mole of phenol area). The water–phenol bonding is lost on one face of the phenol, and this costs ~50 kJ/mol, but this is nearly compensated by the new water–water bonding (~53 kJ/mol of phenol area). The results indicate that the intrinsic bond energy between phenol and Pt(111) is not very different in the gas versus the aqueous phase, provided one takes into consideration the expectation that water forces phenol into islands of high local coverage even at low average coverage (for the same reason that phenol has limited solubility in water). Furthermore, this explains the lack of a strong coverage dependence in the heat of adsorption when it is measured in aqueous phase, whereas it decreases by ~57 kJ/mol with coverage when it is measured in gas phase. This bond-additivity analysis presented here can be easily generalized to other adsorbates, surfaces, and solvents. It clarifies why catalysis with molecules such as phenol which have very strong bonding to Pt-group metals can proceed rapidly at room temperature in liquid solvents such as water but would never proceed in the gas phase at room temperature due to irreversible site poisoning.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Guided Lithium Metal Deposition and Improved Lithium Coulombic Efficiency through Synergistic Effects of LiAsF 6 and Cyclic Carbonate Additives

Spatial and morphology control over lithium (Li) metal nucleation/growth, as well as improving Li Coulombic efficiency (CE) are of the most challenging issues for rechargeable Li metal batteries. Here, we report that LiAsF6 and vinylene carbonate (VC) can work synergistically to address these challenges. It is revealed that AsF6- can be reduced to Li3As and LiF, which can act as seeds for Li growth and form a robust solid electrolyte interphase (SEI) layer, respectively. The addition of VC is critical because it not only enables uniform AsF6- reduction by passivating the defect sites on Cu substrate, but also improves the SEI layer flexibility during the reductive polymerization process. As a result, highly compact, uniform and dendrite-free Li film with vertically aligned columns structure can be obtained with greatly increased Li CE, and the Li metal batteries using the electrolyte with both LiAsF6 and VC additives can have much improved cycle life.

Coulombic efficiency↗