Unraveling the Mechanism and Practical Implications of the Sol-Gel Synthesis of Spinel LiMn2O4 as a Cathode Material for Li-Ion Batteries: Critical Effects of Cation Distribution at the Matrix Level.

Spinel LiMn2O4 (LMO) is a state-of-the-art cathode material for Li-ion batteries. However, the operating voltage and battery life of spinel LMO needs to be improved for application in various modern technologies. Modifying the composition of the spinel LMO material alters its electronic structure, thereby increasing its operating voltage. Additionally, modifying the microstructure of the spinel LMO by controlling the size and distribution of the particles can improve its electrochemical properties. In this study, we elucidate the sol-gel synthesis mechanisms of two common types of sol-gels (modified and unmodified metal complexes)-chelate gel and organic polymeric gel-and investigate their structural and morphological properties and electrochemical performances. This study highlights that uniform distribution of cations during sol-gel formation is important for the growth of LMO crystals. Furthermore, a homogeneous multicomponent sol-gel, necessary to ensure that no conflicting morphologies and structures would degrade the electrochemical performances, can be obtained when the sol-gel has a polymer-like structure and uniformly bound ions; this can be achieved by using additional multifunctional reagents, namely cross-linkers.

Long-term clinical study and multiscale analysis of in vivo biodegradation mechanism of Mg alloy.

There has been a tremendous amount of research in the past decade to optimize the mechanical properties and degradation behavior of the biodegradable Mg alloy for orthopedic implant. Despite the feasibility of degrading implant, the lack of fundamental understanding about biocompatibility and underlying bone formation mechanism is currently limiting the use in clinical applications. Herein, we report the result of long-term clinical study and systematic investigation of bone formation mechanism of the biodegradable Mg-5wt%Ca-1wt%Zn alloy implant through simultaneous observation of changes in element composition and crystallinity within degrading interface at hierarchical levels. Controlled degradation of Mg-5wt%Ca-1wt%Zn alloy results in the formation of biomimicking calcification matrix at the degrading interface to initiate the bone formation process. This process facilitates early bone healing and allows the complete replacement of biodegradable Mg implant by the new bone within 1 y of implantation, as demonstrated in 53 cases of successful long-term clinical study.

Coronary Artery Fistulas: Pathophysiology, Imaging Findings, and Management.

Coronary artery fistulas (CAFs) are abnormal communications of coronary arteries whereby venous circuits bypass the normal capillaries within the myocardium. CAFs are rare, and most affected patients are asymptomatic. However, these fistulas are the most common coronary artery anomalies that can alter coronary hemodynamic parameters. Although most CAFs are asymptomatic in young patients, symptoms and complications become more frequent with increasing age. CAFs are characterized by variable clinical manifestations that are based on the size, origin, and drainage site of the fistula. In symptomatic cases, surgical ligation or percutaneous transcatheter closure is often recommended. Although CAFs historically have been evaluated with conventional invasive angiography, electrocardiographically gated cardiac computed tomographic (CT) angiography has emerged as the noninvasive alternative modality of choice owing to the high spatial and temporal resolution and short acquisition time. Furthermore, three-dimensional volume-rendered CT angiograms facilitate accurate assessment of the complex anatomy of CAFs, including their origin, drainage site, and complexity and the number and size of fistulous tracts. Knowledge of these characteristics is crucial for therapeutic planning. Radiologists must be aware of the pathophysiology, clinical manifestations, and characteristic CT angiographic findings of CAFs; appropriate CT angiographic protocols for evaluation of various CAFs; and the role of CT angiography in preprocedural planning and follow-up. Online supplemental material is available for this article. ©RSNA, 2018.

Solidification Rate Dependence of Microstructures and Transformation Behavior of Ti-Ni-Hf Alloys.

The microstructures and transformation behavior of Ti-49Ni-20Hf, Ti-49.5Ni-20Hf and Ti-50.3Ni- 20Hf alloys, when prepared by conventional casting, were investigated and compared with the properties of the alloys prepared by melt spinning. The area fraction of (Ti,Hf)2Ni in Ti-Ni-Hf alloys decreased to 3.9% from 9.4% as Ni content rose to 50.3 at% from 49 at%. Several cracks were observed in the hot-rolled Ti-49Ni-20Hf alloy sheet but none were found in the Ti-50.3Ni-20Hf alloy sheet. The B2-B19' transformation start temperature (Ms) decreased to 476 K from 580 K as Ni content increased to 50.3 at% from 49 at%. All the as-spun ribbons were amorphous, and the activation energy for crystallization ranged from 167.8 kJ/mol to 182.7 kJ/mol based on Ni content. When annealing temperature ranged from 810 K to 873 K, crystalline Ti-Ni-Hf alloys without (Ti,Hf)2Ni particles were obtained. At annealing temperatures higher than 873 K, very fine (Ti,Hf)2Ni particles, less than 20 nm in size, were found embedded in a crystalline matrix.

Crystallization and Martensitic Transformation Behavior of Ti-Ni-Si Alloy Ribbons Prepared via Melt Spinning.

Ti-(50-x)Ni-xSi (at%) (x = 0.5, 1.0, 3.0, 5.0) alloy ribbons were prepared via melt spinning and their crystallization procedure and transformation behavior were investigated using differential scanning calorimtry, X-ray diffraction, and transmission electron microscopy. Ti-Ni-Si alloy ribbons with Si content less than 1.0 at% were crystalline, whereas those with Si content more than 3.0 at% were amorphous. Crystallization occurred in the sequence of amorphous →B2 → B2 → Ti5Si4 + TiNi3 → B2 + Ti5Si4 + TiNi3 + TiSi in the Ti-47.0Ni-3.0Si alloy and amorphous →R → R + Ti5Si4 + TiNi3 → R + Ti5Si4 + TiNi3 + TiSi in the Ti-45.0Ni-5.0Si alloy. The activation energy for crystallization was 189 ±8.6 kJ/mol for the Ti-47Ni-3Si alloy and 212±8.6 kJ/mol for the Ti-45Ni-5Si alloy. One-stage B2-R transformation behavior was observed in Ti-49.5Ni-0.5Si, Ti-49.0Ni-1.0Si, and Ti-47.0Ni- 3.0Si alloy ribbons after heating to various temperatures in the range of 873 K to 1073 K. In the Ti-45.0Ni-5.0Si alloy, one-stage B2-R transformation occurred after heating to 893 K, two-stage B2-R-B19' occurred after heating to 973 K, and two-stage B2-R-B19' occurred on cooling and one-stage B19'-B2 occurred on heating, after heating to 1073 K.

Investigating Self-Centering Capacity of Superelastic Shape Memory Alloy Fibers with Different Anchorages Through Pullout Tests.

This study investigated the pull-out resistance of superelastic shape memory alloy (SMA) short fibers in mortar with consideration of various end-anchorages that provide different anchoring actions. For the purpose, four types of SMA fibers were prepared using NiTi SMA wires with a diameter of 1.0 mm and the following four end shapes: straight (ST), L-shaped (LS), N-shaped (NS), and spearhead-shaped (SH). The straight-ended fiber was a reference with no working on the end, and the fiber with the spearhead-shaped end was crimped to make the end part flat. The fibers with L- and N-shaped ends were bent with single or double bending. The results showed that only the spearhead-shaped fibers showed self-centering behavior because of the superelasticity of the SMA after slip occurred. This paper discusses the reasons that the ST, LS, and NS fibers do not show self-centering behavior and proposes a concept to induce superelastic behavior in SMA fibers in mortar or concrete.

High performance enzyme fuel cells using a genetically expressed FAD-dependent glucose dehydrogenase α-subunit of Burkholderia cepacia immobilized in a carbon nanotube electrode for low glucose conditions.

FAD-dependent glucose dehydrogenase (FAD-GDH) of Burkholderia cepacia was successfully expressed in Escherichia coli and subsequently purified in order to use it as an anode catalyst for enzyme fuel cells. The purified enzyme has a low Km value (high affinity) towards glucose, which is 463.8 µM, up to 2-fold exponential range lower compared to glucose oxidase. The heterogeneous electron transfer coefficient (Ks) of FAD-GDH-menadione on a glassy carbon electrode was 10.73 s(-1), which is 3-fold higher than that of GOX-menadione, 3.68 s(-1). FAD-GDH was able to maintain its native glucose affinity during immobilization in the carbon nanotube and operation of enzyme fuel cells. FAD-GDH-menadione showed 3-fold higher power density, 799.4 ± 51.44 µW cm(-2), than the GOX-menadione system, 308.03 ± 17.93 µW cm(-2), under low glucose concentration, 5 mM, which is the concentration in normal physiological fluid.

Protection effect of ZrO2 coating layer on LiCoO2 thin film fabricated by DC magnetron sputtering.

Bare and ZrO2-coated LiCoO2 thin films were fabricated by direct current magnetron sputtering method on STS304 substrates. Deposited both films have a well-crystallized structure with (003) preferred orientation after annealing at 600 degrees C. The ZrO2-coated LiCoO2 thin film provide significantly improved cycling stability compared to bare LiCoO2 thin film at high cut-off potential (3.0-4.5 V). The improvement in electrochemical stability is attributed to the structural stability by ZrO2 coating layer.

Effect of precursor supply on structural and morphological characteristics of fe nanomaterials synthesized via chemical vapor condensation method.

Various physical, chemical and mechanical methods, such as inert gas condensation, chemical vapor condensation, sol-gel, pulsed wire evaporation, evaporation technique, and mechanical alloying, have been used to synthesize nanoparticles. Among them, chemical vapor condensation (CVC) has the benefit of its applicability to almost all materials because a wide range of precursors are available for large-scale production with a non-agglomerated state. In this work, Fe nanoparticles and nanowires were synthesized by chemical vapor condensation method using iron pentacarbonyl (Fe(CO)5) as the precursor. The effect of processing parameters on the microstructure, size and morphology of Fe nanoparticles and nanowires were studied. In particular, we investigated close correlation of size and morphology of Fe nanoparticles and nanowires with atomic quantity of inflow precursor into the electric furnace as the quantitative analysis. The atomic quantity was calculated by Boyle's ideal gas law. The Fe nanoparticles and nanowires with various diameter and morphology have successfully been synthesized by the chemical vapor condensation method.

The effects of substrate and annealing on structural and electrochemical properties in LiCoO2 thin films prepared by DC magnetron sputtering.

LiCoO2 thin films were fabricated by direct current magnetron sputtering method on STS304 and Ti substrates. The effects of substrate and annealing on their structural and electrochemical properties of LiCoO2 thin film cathode were studied. Crystal structures and surface morphologies of the deposited films were investigated by X-ray diffraction and field emission scanning electron microscopy. The as-deposited films on both substrates have amorphous structure. The (104) oriented perfect crystallization was obtained by annealing over 600 degrees C in STS304 substrate. The LiCoO2 thin film deposited on Ti substrate shows the (003) texture after annealing at 700 degrees C. The electrochemical properties were investigated by the cyclic voltammetry and charge-discharge measurement. The 600 degrees C-annealed LiCoO2 film deposited on STS304 substrate exhibits the inithial discharge capacity of 22 uAh/cm2 and the 96% capacity retention rate at 50th cycles. The electrochemical measurement on annealed films over 600 degrees C was impossible due to the formed TiO2 insulator layer using Ti substrate. As a result, it was found that the STS304 substrate seems to be more suitable material than the Ti substrate in fabricating LiCoO2 thin film cathode.

Influences of Ti film thickness on electrochemical properties of Si/Ti/Cu film electrodes.

Si and Si/Ti films were fabricated on a Cu current collector (substrate) using the DC sputtering system. The Ti film as a buffer layer was inserted between the Si film and the Cu current collector. Their structural and electrochemical properties were investigated with various Ti film thicknesses of 20-90 nm. The Si and Ti films deposited on a polycrystalline Cu substrate were amorphous. The Si/Ti/Cu film electrode exhibited better electrochemical properties than the Si/Cu electrode in terms of capacity, charge-discharge efficiency, and cycleability. In the Si/Ti/Cu electrode, the film electrode with a 55 nm Ti film thickness showed the best electrochemical properties: 367 microA h/cm2 initial capacity, 91% efficiency, and 50% capacity retention after 100 cycles. These good electrochemical properties are attributed to the enhanced adhesion between the Si and Ti films. Additionally, the modified surface morphology of Si film with a cluster structure could withstand the lateral volume change during the charge-discharge process.

Comparison of Two pMDIs in Adult Asthmatics: A Randomized Double-Blind Double-Dummy Clinical Trial.

BACKGROUND: Only a few studies directly compared the therapeutic efficacy and safety of two pressurized metered-dose inhalers (pMDIs) in asthma. We analyzed the asthma treatment outcomes, safety, and patient preferences using formoterol/beclomethasone (FORM/BDP), a pMDI with extra-fine particles, compared with formoterol/budesonide (FORM/BUD), another pMDI with non-extra-fine particles. METHODS: In this randomized, double-blind, double-dummy parallel group study, 40 adult asthmatics were randomized to FORM/BDP group (n=18; active FORM/BDP and placebo FORM/BUD) or FORM/BUD group (n=22; active FORM/BUD and placebo FORM/BDP). During the two visits (baseline and end of 8-week treatment), subjects were asked to answer questionnaires including asthma control test (ACT), asthma control questionnaires (ACQ), and Quality of Life Questionnaire for Adult Korean Asthmatics (QLQAKA). Lung function, compliance with inhaler, and inhaler-handling skills were also assessed. RESULTS: Ten subjects in the FORM/BDP group and 14 in the FORM/BUD group completed follow-up visits. ACT, ACQ, QLQAKA (a primary outcome), and adverse events did not differ between two groups. We found that the increase in forced expiratory volume in 1 second/forced vital capacity and forced expiratory flow at 25% to 75% of the pulmonary volume in the FORM/BDP group was higher than in the FORM/BUD group. Regarding preference, subjects responded that the flume velocity of FORM/BDP was higher, but more adequate than that of FORM/BUD. They also answered that FORM/BDP reached the trachea and bronchus and irritated them significantly more than FORM/BUD. CONCLUSION: The use of pMDI with extra-fine particles may relieve small airway obstruction more than the one with non-extra-fine particles despite no significant differences in overall treatment outcomes. Some asthmatics have a misconception about the adequacy of high flume velocity of pMDIs.

Electrochemical characteristics with the addition of carbon nanotubes and the manufacturing process for sulfur cathode in the Li/S cell.

Carbon nanotubes (CNTs) were purified using acid solution, and CNT-sulfur composite powder was prepared via precipitation, using the purified CNTs. In addition, the effect of the purified CNTs (PUCNTs) on the electrochemical performance of the Li/S cell was investigated. After the purification, almost all the impurities in the as-synthesized CNTs (ASCNTs) were removed, and the dispersibility of the CNTs was improved. On the other hand, the concentration of the structural defects and of the disordered structures in the PUCNTs was increased due to the surface oxidation of the tubes during acid treatment. In the case of the PUCNT-S composite powder, the outer wall of the tubes was well covered with sulfur, as opposed to the tubes in the ASCNT-S composite powder. The Li/S cell containing ASCNT-S composite cathode showed a large voltage decrease and a 680 mAh/g capacity during the first discharge process. The Li/S cell with PUCNT-S composite cathode, however, showed a higher discharge capacity and better cycle performance than the cell with ASCNT-S composite cathode. The electrochemical performance of the Li/S cell was improved for the PUCNT-S composite cathode using the CNTs purified by acid treatment.

Effect of Thermal Cycling on Transformation Behavior of Ti-24Nb-1Mo Alloy (at.%).

The effect of thermal cycling on the transformation behavior of a Ti-24Nb-1Mo alloy was investigated by means of electrical resistivity measurement, transmission electron microscopy (TEM), X-ray diffraction (XRD), tensile test and Vickers hardness tests. Electrical resistivity changes were not observed in all alloys. It indicates that thermally induced martensitic transformation does not take place in the alloys. After thermal cycling between 298 K and 77 K, clear X-ray diffraction peaks corresponding to ωath phase, which did not exist before thermal cycling, were observed. Volume fraction of ωath phase increased as increasing the number of thermal cycling. ωath phase formed during thermal cycling increased hardness of the alloy. Although thermally induced martensitic transformation did not occur in the alloys, superelastic deformation behavior was observed in the alloys. The superelastic recovery ratio decreased from 81% to 41% by increasing the number of thermal cycling, which came from the increase in the volume fraction of ωath phase.

The Effect of Crystal Structure on the Growth of Nanotubular Oxide Layers Formed on Ti-Ni Alloys.

Electrochemical anodization of Ti-Ni alloys with different Ni composition was carried out in an ethylene glycol base electrolyte under the various conditions to investigate the effect of crystal structure and chemical composition of the Ti-Ni alloy. X-ray diffraction patterns indicated that Ti-48.0 Ni and Ti-49.0Ni alloys were the martensitic phase at room temperature, while Ti 50.6Ni and 51.0Ni were the austenitic phase. Self-organized nanotubular oxide layers were formed on four Ti-Ni alloys. The thickness of oxide layers increased with increasing anodization time and applied voltages. Energy-dispersive X-ray analysis indicated that the nanotubular oxide layers consist of two kinds of oxides, one of which is Titanium oxide and the other is Nickel oxide. These results indicate that the growth of nanotubular oxide layer formed Ti-Ni alloys are not affected by crystal structure, but by applied voltage and anodization time.

Free-Standing NiS2 Electrode as High-Rate Anode Material for Sodium-Ion Batteries.

Owing to the speculated price hike and scarcity of lithium resources, sodium-ion batteries are attracting significant research interest these days. However, sodium-ion battery anodes do not deliver good electrochemical performance, particularly rate performance. Herein, we report the facile electrospinning synthesis of a free-standing nickel disulfide (NiS²) embedded on carbon nanofiber. This electrode did not require a conducting agent, current collector, and binder, and typically delivered high capacity and rate performance. The electrode delivered a high initial capacity of 603 mAh g-1 at the current density of 500 mA g-1. Moreover, the electrode delivered the capacity of 271 mAh g-1 at the high current density of 15 A g-1. The excellent rate performance and high coulombic efficiency of the electrode were attributed to its low charge transfer resistance and unique structure.

Catalytic growth and structural characterization of semiconducting beta-Ga2O3 nanowires.

We have successfully synthesized beta-Ga2O3 nanomaterials with various morphologies, such as wire, rod, belt and sheet-like, through simple thermal evaporation of metal gallium powder in the presence of nickel oxide catalyst. beta-Ga2O3 nanomaterials with different morphology were observed as a function of synthesis time and temperature. In this report, generation sites of the beta-Ga2O3 nanomaterials have been delicately surveyed by FESEM. The growth mechanisms of nanomaterials are distinguished by the view of its generation site. The growth of nanowire follows both VLS and VS mechanism and other kinds of materials such as nanorod, nanobelt and nanosheet follows VS mechanism.

Shape memory characteristics and superelasticity of Ti-Ni-Cu alloy ribbons with nano Ti2Ni particles.

Microstructures and deformation behaviour of Ti-45Ni-5Cu and Ti-46Ni-5Cu alloy ribbons prepared by melt spinning were investigated by transmission electron microscopy, thermal cycling tests under constant load and tensile tests. Spherical Ti2Ni particles coherent with the B2 parent phase were observed in the alloy ribbons when the melt spinning temperature was higher than 1773 K. Average size of Ti2Ni particles in the ribbons obtained at 1873 K was 8 nm, which was smaller than that (10 nm) in the ribbons obtained at 1773 K. Volume fraction of Ti2Ni phase in the ribbons obtained at 1873 K was 40%, which was larger than that (20%) in the ribbons obtained at 1773 K. The stress required at temperatures of Af + 10 K for the stress-induced martensitic transformation increased from 93 MPa to 229 MPa and apparent elastic modulus of the B2 parent phase increased from 56 GPa to 250 GPa with increasing the melt spinning temperature from 1673 K to 1873 K in Ti-45Ni-5Cu alloy ribbons. The critical stress for slip deformation of the ribbons increased by coherent Ti2Ni particles, and thus residual elongation did not occur even at 160 MPa, while considerable plastic deformation occurred at 60 MPa in the ribbons without Ti2Ni particles. Almost perfect superelastic recovery was found in the ribbons with coherent Ti2Ni particles, while only partial superelastic recovery was observed in the ribbons without coherent Ti2Ni particles.