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At least 811 records · Page 45

Hollow Fibers Structured Packings in Olefin/Paraffin Distillation: Apparatus Scale-Up and Long-Term Stability

Following the conceptual demonstration of high separation efficiency and column capacity obtained in olefin/paraffin distillation using hollow fiber structured packings (HFSPs) in a bench scale (J. Membr. Sci.2006, 2007, and 2010), we scaled-up this process with a 10-fold increase in the internal flow rate and a 3-fold increase in the module length. We confirmed that the HFSPs technology gives high separation efficiency and column capacity in iso-/n-butane distillation for 18 months. We systematically investigated the effects of packing density, concentration of light component, reflux ratio, and module age on the separation efficiency and operating stability. The comprehensive characterizations using scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) were carried out to probe the changes in the morphological, thermal, and mechanical properties of polypropylene (PP) hollow fibers over the aging process. Our results suggest that after a long-term exposure to light hydrocarbon environments at ≤70 °C the morphological and mechanical properties of the PP polymer do not degrade significantly in a propane/propylene and iso-/n-butane environment.

36 MATERIALS SCIENCE↗

Study on Nanocellulose Properties Processed Using Different Methods and Their Aerogels

In this paper the effects of different mechanical methods including homogenization, ultrasonication and grinding on the properties of the nanocellulose materials and their aerogels, were investigated. The cellulose nanocrystal products, (CNC-H) and (CNC-U), were prepared by homogenization and ultrasonication of the acid hydrolyzed pulps, respectively. The aerogel products were produced by solvent exchanging of nanocellulose hydrogels with tertiary butyl alcohol and followed by freeze drying. The nanocellulose materials were studied using transmission electron microscopy, field emission scanning electron microscopy (FE-SEM), Fourier transformed infrared spectroscopy (TEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA). Size distribution and surface charges of the nanocellulose suspensions were measured by zetasizer. Also, the morphology, the porosity properties and surface area of the CNCs and CNF aerogels were investigated via FE-SEM and nitrogen adsorption–desorption isotherms. The results showed that CNC-H has higher surface charge, suspension stability (− 41.8 mV), crystallinity index (74.7%) and better size dispersion than CNC-U and CNF with an average particle size of 122 nm. CNC-H microstructures demonstrated homogeneous network structure with smaller nanometer dimensions (15–30 nm width and 60–400 nm length). However, the CNC-H showed lower thermal stability compared to CNC-U and CNF. Larger average pore size (16.32 nm), pore volume (0.42 cc/g) and high specific surface area (> 100 m{sup 2} g{sup −1}) in CNC-H aerogel were obtained. Graphical Abstract: Suspensions of nanocellulose (NC) were prepared by different mechanical methods: Homogenizing, Ultrasonic and grinding. The NC products were investigated and their differences in morphology and other characteristics were studied. The aerogels were prepared from the nanocellulose hydrogels. The nitrogen physisorption was used to study the pore characteristics of the aerogels. .

36 MATERIALS SCIENCE↗

Photo-Crosslinkable Naphthalene Diimide Polymer for Solution-Processed n – i – p Perovskite Solar Cells

We copolymerize a norbornene monomer bearing a pendant naphthalene diimide with a norbornene bearing a cinnamate pendant moiety to synthesize a crosslinkable electron-transporting polymer and study its use in solution-processed n–i–p perovskite solar cells. The crosslinked material exhibits over 90% transparency in the visible region and higher thermal stability (>300 °C) and lower surface energy than the corresponding homopolymer of the naphthalene diimide functionalized norbornene. Coating an ITO surface with the photo-crosslinked copolymer yields a slightly lower work function than homopolymer-coated ITO. We show that the morphologies of the perovskite films deposited on both polymers are similar (~300 nm features) based upon scanning electron microscopy. Our solar-cell device results show that the crosslinked naphthalene diimide polymer gives a higher open-circuit voltage (1.08 vs 1.05 V), fill factor (average 64.43 vs 58.77%), and stabilized power conversion efficiency (12.28 vs 10.33%) compared to its non-crosslinked homopolymer counterpart, as well as reduced hysteresis. As a result, we attribute the improved performance to decreased work function, reduced nonradiative recombination, and higher shunt resistance.

14 SOLAR ENERGY↗

MnO{sub 2}@colloid carbon spheres nanocomposites with tunable interior architecture for supercapacitors

Graphical abstract: - Highlights: • MnO{sub 2}@CSs nanocomposites have been successfully synthesized in room temperature. • The composites exhibited three structures: core–shell, yolk–shell and hollow structure. • The yolk–shell structure exhibited a high specific capacitance and cycling stability. - Abstract: MnO{sub 2}@colloid carbon spheres nanocomposites with tunable interior architecture have been synthesized by a facile and cost-effective strategy at room temperature. The structure and morphology of as-prepared nanocomposites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption, focused ion beam scanning electron microscopy (FIB/SEM) and high-resolution transmission electron microscopy (HRTEM). The as-obtained composites exhibited a three-dimensional architecture with core–shell, yolk–shell and hollow interior structure. Furthermore, the electrochemical properties of composites were evaluated by cycle voltammetric (CV) and galvanostatic charge–discharge measurements. The yolk–shell structure exhibited the optimized pseudocapacitance performance, revealing a specific capacitance (273 F g{sup −1}) with a good rate and cycling stability, owing to its unique structure and the poor crystallinity of MnO{sub 2} nanofilms. Therefore, this facile synthetic strategy could be useful to design and synthesis of tunable nanostructures with enhanced supercapacitor behavior.

36 MATERIALS SCIENCE↗

Low temperature solid-state synthesis of nanocrystalline gallium nitride

Graphical abstract: Display Omitted Highlights: ► GaN nanocrystalline was prepared via a solid-state reacion at relatively low temperature. ► The sizes and crystallinities of the GaN samples obtained at the different temperatures are investigated. ► The GaN sample has oxidation resistance and good thermal stability below 1000 °C. -- Abstract: Nanocrystalline gallium nitride was synthesized by a solid-state reaction of metallic magnesium powder, gallium sesquioxide and sodium amide in a stainless steel autoclave at a relatively low temperature (400–550 °C). The structures and morphologies of the obtained products were derived from X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). XRD patterns indicated that the products were hexagonal GaN (JCPDS card no. 76-0703). The influence of reaction temperature on size of the products was studied by XRD and TEM. Furthermore, the thermal stability and oxidation resistance of the nanocrystalline GaN were also investigated. It had good thermal stability and oxidation resistance below 800 °C in air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fuel Cells Catalyst for Start-up and Shutdown Conditions: Electrochemical, XPS, and TEM Evaluation of Sputter-Deposited Ru, Ir, and Ti on Pt-Nano-Structured Thin Film (NSTF) Support

Minute amounts of Ru, Ir and Ti (2 and 10 g/cm2) sputter-deposited over 3M Pt-coated nano-structured thin film (NSTF) substrate were evaluated as oxygen evolution reaction (OER) catalysts in a polymer electrolyte membrane (PEM) environment. The purpose of the study was to explore the suitability of these elements for modifying both the anode and the cathode catalysts in order to lower the overpotential for the oxidation of water during transient conditions. By keeping the electrode potential as close as possible to the thermodynamic potential for OER, other components in the fuel cell, such as platinum, the gas diffusion layer and the bipolar plates, will be less prone to degradation. While Ru and Ir were chosen due to their high OER activity in aqueous environment, Ti was also included due to its ability to stabilize the OER catalysts. The 3M Pt-NSTF was selected as a stable, carbon-free substrate. The surface chemistry and the morphology of OER catalysts on Pt-NSTF were examined by x-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The OER catalytic activity of Ru and Ir in PEMs compares well with their behavior in aqueous environment. It was found that Ru is more active than Ir, that Ir is considerably more stable, while the mass activity of both is higher in comparison with similar OER catalyst.

OER↗

Facile approach to prepare hollow core–shell NiO microspherers for supercapacitor electrodes

A facile lamellar template method (see image) has been developed for the preparation of uniform hollow core–shell structure NiO (HCS–NiO) with a nanoarchitectured wall structure. The prepared NiO was found to be highly crystalline in uniform microstructures with high specific surface area and pore volume. The results indicated that ethanol interacted with trisodium citrate played an important role for the formation of hollow core–shell spheres. On the basis of the analysis of the composition and the morphology, a possible formation mechanism was investigated. NiO microspheres with hollow core–shell showed excellent capacitive properties. The exceptional cyclic, structural and electrochemical stability with ∼95% coulombic efficiency, and very low ESR value from impedance measurements promised good utility value of hollow core–shell NiO material in fabricating a wide range of high-performance electrochemical supercapacitors. - The hollow core–shell NiO was prepared with a facile lamellar template method. The prepared NiO show higher capacitance, lower ion diffusion resistance and better electroactive surface utilization for Faradaic reactions. - Highlights: • Formation of hollow core–shell NiO via a novel and facile precipitation route. • Exhibited uniform feature sizes and high surface area of hollow core–shell NiO. • Synthesized NiO has high specific capacitance ( 448 F g{sup 1}) and very low ESR value. • Increased 20% of long life cycles capability after 500 charge–discharge cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electroconvection near an ion-selective surface with Butler–Volmer kinetics

We study the effects of interfacial kinetics on the electro-hydrodynamics of ion transport near an ion-selective surface using a combination of linear stability analysis and numerical simulation. The finite kinetics of the electrolyte–electrode interface affects the ion transfer and electroconvection in many ways. On a surface of fixed topography, such as a metal surface of slow and stable ion deposition or covered by a polymer membrane, the finite kinetics reduces the current in one-dimensional ion diffusion/migration, increases the critical voltage for the onset of the electroconvective instability, changes the dynamics of the electroconvection and the overlimiting current, and enhances the lateral ion diffusion within the interfacial layer. The first three effects are indirectly caused by the reaction kinetics and can be characterized by an effective voltage difference across the liquid electrolyte. In comparison, the last effect is controlled by a direct interplay between kinetics and nonlinear electroconvection. Scaling laws for ion transport and features of electroconvection are proposed. We also analyse the linear stability of a surface which evolves under ion deposition and find that the finite kinetics decreases the growth rate of both electroconvective and morphological instabilities and therefore modifies the wavenumber of the most unstable mode.

Mechanics↗

A Carbonyl and Azo-Based Polymer Cathode for Low-Temperature Na-Ion Batteries

Due to flexible structure tunability and abundant structure diversity, redox-active polymers are promising cathode materials for developing affordable and sustainable Na-ion batteries (NIBs). However, polymer cathodes still suffer from low capacity, poor cycle life, and sluggish reaction kinetics. Herein, we designed and synthesized a polymer cathode material bearing carbonyl and azo groups as well as extended conjugation structures in the repeating units. The polymer cathode exhibited exceptional electrochemical performance in NIBs in terms of high capacity, long lifetime, and fast kinetics. When coupled with a low-concentration electrolyte, it shows superior performance at low temperatures down to -50 °C, demonstrating great promise for low-temperature battery applications. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were employed to study the reaction mechanism, interphase structure, and morphological evolution, confirming reversible redox reactions between azo/carbonyl groups in the polymer and Na + /electrons, a NaF-rich interphase, and high structure stability upon cycling. In conclusion, this work provides an effective approach to developing high-performance polymer cathodes for affordable, sustainable, and low-temperature NIBs.

25 ENERGY STORAGE↗

Microwave-Based Synthesis of Functional Morphological Variants and Carbon Nanotube-Based Composites of VS 4 for Electrochemical Applications

A novel facile, fast, and efficient microwave-assisted method was developed to synthesize a number of diverse nanostructured motifs (ranging from nanorods to nanoflowers) of VS 4 along with its associated composite heterostructures, VS 4 /multi-walled carbon nanotube (MWNT; i.e., multi-walled carbon nanotubes). Specifically, we have probed and correlated the effects of a number of specific experimental variables, including primarily precursor, solvent, temperature, and time. We noted that nanorods formed more readily with VO(acac) 2 as the vanadium precursor and n-methyl-2-pyrrolidone (NMP) as a polar reaction solvent. By contrast, we determined that hierarchical three-dimensional (3D) nanoflower-like assemblies, ranging in size from 100 to 200 nm in average diameter, could be controllably synthesized by using Na 3 VO 4 as the vanadium precursor and an aqueous water: polar solvent mixture as the reaction medium. We also observed that VS 4 disintegrates, when in the presence of either air, solution, or a combination of these environments, and established that the extent of VS4 nanorod decomposition could be almost fully prevented by storage under nitrogen. From an application’s perspective, our VS 4 is electrochemically active and shows behavior, consistent with the literature. In particular, as compared with pristine VS 4 nanorods alone, we observed enhanced electrochemical activity with (i) 3D hierarchical flower-like motifs, (ii) unique necklace-like VS 4 nanorod–MWNT composites, and (iii) samples in which as-prepared VS4 nanorods had been annealed. Moreover, we found that the rational application of specific physical and chemical processing treatments, such as (i) thermal annealing to improve crystallinity, (ii) the addition of MWNTs to form conductive composites, and (iii) the evolution of morphology from one-dimensional (1D) nanorods to more complex 3D nanoflowers, was favorable to the resulting electrochemical performance with respect to increasing stability and reversibility.

25 ENERGY STORAGE↗

Assembly of multi-flavored two-dimensional colloidal crystals

We systematically investigate the assembly of binary multi-flavored colloidal mixtures in two dimensions. In these mixtures all pairwise interactions between species may be tuned independently. This introduces an additional degree of freedom over more traditional binary mixtures with fixed mixing rules, which is anticipated to open new avenues for directed self-assembly. At present, colloidal self-assembly into non-trivial lattices tends to require either high pressures for isotropically interacting particles, or the introduction of directionally anisotropic interactions. Here we demonstrate tunable assembly into a plethora of structures which requires neither of these conditions. We develop a minimal model that defines a three-dimensional phase space containing one dimension for each pairwise interaction, then employ various computational techniques to map out regions of this phase space in which the system self-assembles into these different morphologies. We then present a mean-field model that is capable of reproducing these results for size-symmetric mixtures, which reveals how to target different structures by tuning pairwise interactions, solution stoichiometry, or both. Concerning particle size asymmetry, we find that domains in this model's phase space, corresponding to different morphologies, tend to undergo a continuous “rotation” whose magnitude is proportional to the size asymmetry. Such continuity enables one to estimate the relative stability of different lattices for arbitrary size asymmetries. Owing to its simplicity and accuracy, we expect this model to serve as a valuable design tool for engineering binary colloidal crystals from multi-flavored components.

Mahynski, Nathan A.↗

Enhanced field emission from cerium hexaboride coated multiwalled carbon nanotube composite films: A potential material for next generation electron sources

Intensified field emission (FE) current from temporally stable cerium hexaboride (CeB{sub 6}) coated carbon nanotubes (CNTs) on Si substrate is reported aiming to propose the new composite material as a potential candidate for future generation electron sources. The film was synthesized by a combination of chemical and physical deposition processes. A remarkable increase in maximum current density, field enhancement factor, and a reduction in turn-on field and threshold field with comparable temporal current stability are observed in CeB{sub 6}-coated CNT film when compared to pristine CeB{sub 6} film. The elemental composition and surface morphology of the films, as examined by scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray measurements, show decoration of CeB{sub 6} nanoparticles on top and walls of CNTs. Chemical functionalization of CNTs by the incorporation of CeB{sub 6} nanoparticles is evident by a remarkable increase in intensity of the 2D band in Raman spectrum of coated films as compared to pristine CeB{sub 6} films. The enhanced FE properties of the CeB{sub 6} coated CNT films are correlated to the microstructure of the films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Buoyancy effects on morphological instability during directional solidification

The onset of morphological instability during the directional solidification of a single-phase binary alloy at constant velocity vertically upwards is treated by a linear stability analysis. The case in which a heavier solute is rejected at the solidifying interface is considered, and the effect of natural convection on the critical concentration for the onset of instability is studied. For tin containing lead, a small destabilization of the system at low growth velocities, and a large increase in the wavelength of the instability at the onset are found. Calculations show that the destabilization is enhanced as the variation of density with solute concentration is reduced, and in the limit of neutrally-dense solute, there is a long wavelength instability for which the critical solute concentration is several orders of magnitude lower than that predicted by the Mullins and Sekerka (1964) analysis in the absence of convection. For the neutrally-dense solute, a simplified analysis indicates the roles played by the interface deformation and thermal convection in promoting the instability. In particular, the destabilization is very sensitive to the ratio of crystal and melt thermal conductivities.

Coriell, S. R.↗

Enhanced Thermal Stability of W-Ni-Al 2 O 3 Cermet-Based Spectrally Selective Solar Absorbers with Tungsten Infrared Reflectors

Solar thermal technologies such as solar hot water and concentrated solar power trough systems rely on spectrally selective solar absorbers. These solar absorbers are designed to efficiently absorb the sunlight while suppressing re-emission of infrared radiation at elevated temperatures. Efforts for the development of such solar absorbers must not only be devoted to their spectral selectivity but also to their thermal stability for high temperature applications. In this work, selective solar absorbers based on two cermet layers are fabricated on mechanically polished stainless steel substrates using a magnetron sputtering technique. The targeted operating temperature is 500–600 °C. A detrimental change in the morphology, phase, and optical properties is observed if the cermet layers are deposited on a stainless steel substrate with a thin nickel adhesion layer, which is due to the diffusion of iron atoms from the stainless steel into the cermet layer forming a FeWO 4 phase. In order to improve thermal stability and reduce the infrared emittance, tungsten is found to be a good candidate for the infrared reflector layer due to its excellent thermal stability and low infrared emittance. Lastly, a stable solar absorptance of ≈0.90 is demonstrated, with a total hemispherical emittance of 0.15 at 500 °C.

14 SOLAR ENERGY↗

Morphological instability in rapid directional solidification

Mullins and Sekerka (1964) showed for fixed temperature gradient that the planar interface is linearly stable for all pulling speeds V above some critical value, the absolute stability limit. Near this limit, where solidification rates are rapid, the assumption of local equilibrium at the interface may be violated. Here, nonequilibrium effects are incorporated into a linear stability analysis of the planar front by allowing the segregation coefficient and interface temperature to depend on V in a thermodynamically consistent way. The absolute stability limit of the cellular mode is modified. A new oscillatory state is formed which, in the absence of latent heat, has a critical wavenumber of zero; by itself this instability would lead to the formation of solute bands in the solid. This mode has its own absolute-stability limit determined by solute trapping and kinetics. Under certain conditions, there exists a window of stability above the steady absolute-stability boundary and below the oscillatory-stability boundary; here the planar segregation-free state is restabilized.

Merchant, G. J.↗

Novel silica stabilization method for the analysis of fine nanocrystals using coherent X-ray diffraction imaging

High-energy X-ray Bragg coherent diffraction imaging (BCDI) is a well established synchrotron-based technique used to quantitatively reconstruct the three-dimensional morphology and strain distribution in nanocrystals. The BCDI technique has become a powerful analytical tool for quantitative investigations of nanocrystals, nanotubes, nanorods and more recently biological systems. BCDI has however typically failed for fine nanocrystals in sub-100?nm size regimes ? a size routinely achievable by chemical synthesis ? despite the spatial resolution of the BCDI technique being 20?30?nm. The limitations of this technique arise from the movement of nanocrystals under illumination by the highly coherent beam, which prevents full diffraction data sets from being acquired. A solution is provided here to overcome this problem and extend the size limit of the BCDI technique, through the design of a novel stabilization method by embedding the fine nanocrystals into a silica matrix. Chemically synthesized FePt nanocrystals of maximum dimension 20?nm and AuPd nanocrystals in the size range 60?65?nm were investigated with BCDI measurement at beamline 34-ID-C of the APS, Argonne National Laboratory. Novel experimental methodologies to elucidate the presence of strain in fine nanocrystals are a necessary pre-requisite in order to better understand strain profiles in engineered nanocrystals for novel device development.

36 MATERIALS SCIENCE↗

Mechanistic origin of solvent-dependent thermal stability in sodiated Sn anodes for sodium-ion batteries

Understanding the thermal stability of high-energy density alloy anodes is critical for the safe deployment of sodium-ion batteries (SIBs). Here, accelerating rate calorimetry (ARC), post-mortem characterizations, and density functional theory (DFT) calculations are combined to understand the thermal reactivity of fully sodiated Sn, Sn-hard carbon (HC) blends, and HC anodes in carbonate- and ether-based electrolytes. ARC measurements show that propylene carbonate (PC) causes earlier self-heating rate (SHR) onset and higher reactivity than tetraethylene glycol dimethyl ether (TEGDME), indicating inferior thermal stability. Sodiated Sn exhibits better thermal stability than sodiated HC, while Sn-HC blends show intermediate behavior that improves with increasing Sn content. Post-ARC analyses reveal desodiation of Na15Sn4 to metallic Sn with particle coalescence, whereas Sn-HC blends and HC retain finer morphologies. PC promotes Sn oxidation to SnO, while TEGDME suppresses oxide formation; NaPF6-containing electrolytes additionally form NaF. DFT calculations show that PC adsorption lowers Na extraction energy and enhances interfacial electronic interactions, facilitating Na release and reductive decomposition. These results establish a direct correlation between solvent-dependent reaction pathways and thermal stability in SIB alloy anodes.

Accelerating rate calorimetry↗

Dichlorinated Dithienylethene-Based Copolymers for Air-Stable n-Type Conductivity and Thermoelectricity

Here, two donor-acceptor polymers were obtained by coupling difluoro- and dichloro-substituted forms of the electron-deficient unit BDOPV and the relatively weak donor moiety dichlorodithienylethene (ClTVT). The conductivity and power factors of doped devices are different for the chlorinated and fluorinated BDOPV polymers. High electron conductivity of 38.3 and 16.1 S cm -1 were obtained from the chlorinated and fluorinated polymers with N-DMBI, respectively, and 12.4 and 2.4 S cm -1 were obtained from the chlorinated and fluorinated polymers with CoCp 2 , respectively, from drop-cast devices. The corresponding power factors are 22.7, 7.6, 39.5 and 8.0 μW m -1 K -2 , respectively. Doping of PClClTVT with N-DMBI results in excellent air-stability; the electron conductivity of devices with 50 mol% N-DMBI as dopant remained up to 4.9 S m -1 after 222 days in the air, the longest for an n-doped polymer stored in air, with a thermoelectric power factor of 9.3 μW m -1 K -2 . However, the conductivity of PFClTVT-based devices can hardly be measured after 103 days. These observations are consistent with morphologies determined by grazing incidence wide angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM). The results demonstrate that chemical structures leading to dense and ordered packing can enhance electron conductivity and air stability of n-type donor-acceptor polymers.

30 DIRECT ENERGY CONVERSION↗