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.

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.

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.

Objective assessment of flap volume changes and aesthetic results after adjuvant radiation therapy in patients undergoing immediate autologous breast reconstruction.

BACKGROUND: The use of immediate breast reconstruction and adjuvant radiation therapy is increasing in breast cancer patients. This study aimed to analyze the aesthetic outcome and changes in flap volume in patients with breast cancer undergoing radiation therapy of the surgical site after immediate autologous tissue reconstruction. METHODS: Immediate abdominal free flap breast reconstruction following unilateral mastectomy was performed in 42 patients; 21 patients received adjuvant radiation (study group) and 21 patients did not (control group). To compare flap volume, three-dimensional computed tomography (CT) was performed before and after radiation. Also, aesthetic analysis was performed in both groups to evaluate shape changes. RESULTS: There was a 12.3% flap volume reduction after the completion of radiation in the experimental group that was significantly greater than the 2.6% volume reduction observed in the non-radiation group (P<0.01). There was no significant difference in the short- and long-term aesthetic results between the groups. CONCLUSIONS: When performing immediate autologous breast reconstruction, 14% volume overcorrection is recommended for patients in whom adjuvant radiation therapy is anticipated to improve aesthetic outcomes.

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.

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.

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.

Experiments on deformation behaviour of functionally graded NiTi structures.

Functionally graded NiTi structures benefit from the combination of the smart properties of NiTi and those of functionally graded structures. This article provides experimental data for thermomechanical deformation behaviour of microstructurally graded, compositionally graded and geometrically graded NiTi alloy components, related to the research article entitled "Functionally graded shape memory alloys: design, fabrication and experimental evaluation" (Shariat et al., 2017) [1]. Stress-strain variation of microstructurally graded NiTi wires is presented at different heat treatment conditions and testing temperatures. The complex 4-way shape memory behaviour of a compositionally graded NiTi strip during one complete thermal cycle is demonstrated. The effects of geometrical design on pseudoelastic behaviour of geometrically graded NiTi plates over tensile loading cycles are presented on the stress-strain diagrams.

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.

Compositionally graded Ti-Ni alloys prepared by diffusion bonding.

A Ti-Ni alloy compositionally graded along the thickness direction in order to obtain a shape change over a wide temperature range, which is beneficial to the actuator for precise position control, was prepared by spark plasma sintering (SPS) after stacking Ti-Ni alloy ribbons in the sequence of Ti-51Ni, Ti-50Ni, Ti-49Ni and Ti-48Ni (at%) followed by annealing. Then, the microstructure and martensitic transformation behavior were investigated by using FE-SEM, DSC and thermal cycling tests under a constant load. The inter-ribbon defects observed after SPS due to insufficient diffusional bonding between the ribbons were eliminated by post-SPS annealing at 1023 K for 36 ks. The compositionally graded sample showed compositional variation of 1.5 at% Ti along the thickness direction (- 120 µm) and a martensitic transformation temperature window as large as 91 K on cooling and 79 K on heating. A recoverable elongation of 0.9% was obtained under a stress of 80 MPa and the deformation rate, which is defined as the ratio of the recoverable elongation to the temperature range where the elongation occurred was 0.015%/K in the compositionally graded sample.

Electrochemical properties of Si film electrodes grown on current collectors with CuO nanostructures for thin-film microbatteries.

Si film electrodes were deposited onto Cu foil current collectors fabricated with well-formed CuO nanostructures. The structural and electrochemical properties of the Cu foils oxidized for 1, 3, and 6 h and of the Si film electrodes were investigated using field-emission scanning electron microscopy, X-ray diffraction (XRD), and charge/discharge tests. The morphologies and XRD profiles suggested that the oxidized Cu foils consisted of a top CuO layer and a bottom Cu2O layer. The surface roughness of the Cu foils decreased with increasing oxidation time since the flower-like CuO nanostructures weakly adhered to the surface were easily detached by ultrasonic cleaning. The cycle performance of the Si film electrode with the rougher CuO layer rapidly deteriorated, whereas the flat Cu2O layer showing a relatively high electric conductivity induced the formation of a dense Si film and improved the electrochemical performance of the Si film electrode.

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.

Nullifying tumor efflux by prolonged endolysosome vesicles: development of low dose anticancer-carbon nanotube drug.

As the majority of side effects of current chemotherapies stems from toxicity due to excessive dosing of anticancer drugs, minimizing the amount of drug while maximizing drug efficacy is essential to increase the life-quality of chemotherapy patients. This study demonstrated that the intracellular delivery of amide linked doxorubicin on carbon nanotube can nullify the efflux of cancer cells by achieving prolonged endolysosome delivery and can induce burst release of doxorubicin in an acidic hydrolase environment and, ultimately, can reduce the amount of anticancer drug by 10-fold compared to conventional effective drug dose. The clearance of accumulated carbon nanotubes in the liver was observed after 4 weeks, and analysis of liver toxicity markers showed no significant changes in GOT and GPT levels and release of pro-inflammatory cytokines across both short- and long-term periods.

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.

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.