Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Alternatives for improving energy security in Cape Verde

The lack of consensus on the meaning of energy security and how it should be measured hinders the evaluation of alternatives for improving the Cape Verdean energy sector. The objective of the paper is to develop an energy security index adjusted to the country's context. The methods used are the multi-criteria analysis and the Delphi survey. Different alternatives to improve energy security are assessed: electrically interconnect Cape Verde's islands, increase the share of renewable energy, and a combination of the previous alternatives. The results of our analysis indicate that increasing renewable energy is the optimal alternative for Cape Verde.     

Graphite Oxide and Aromatic Amines: Size Matters

Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”.     

Genetic algorithm and self organizing map based fuzzy hybrid intelligent method for color image segmentation

The grouping of pixels based on some similarity criteria is called image segmentation. In this paper the problem of color image segmentation is considered as a clustering problem and a fixed length genetic algorithm (GA) is used to handle it. The effectiveness of GA depends on the objective function (fitness function) and the initialization of the population. A new objective function is proposed to evaluate the quality of the segmentation and the fitness of a chromosome. In fixed length genetic algorithm the chromosomes have same length, which is normally set by the user. Here, a self organizing map (SOM) is used to determine the number of segments in order to set the length of a chromosome automatically. An opposition based strategy is adopted for the initialization of the population in order to diversify the search process. In some cases the proposed method makes the small regions of an image as separate segments, which leads to noisy segmentation. A simple ad hoc mechanism is devised to refine the noisy segmentation. The qualitative and quantitative results show that the proposed method performs better than the state-of-the-art methods.     

The Interplay of Modulus,Strength, and Ductility in Adhesive Design Using Biomimetic Polymer Chemistry

High‐performance adhesives require mechanical properties tuned to demands of the surroundings. A mismatch in stiffness between substrate and adhesive leads to stress concentrations and fracture when the bonding is subjected to mechanical load. Balancing material strength versus ductility, as well as considering the relationship between adhesive modulus and substrate modulus, creates stronger joints. However, a detailed understanding of how these properties interplay is lacking. Here, a biomimetic terpolymer is altered systematically to identify regions of optimal bonding. Mechanical properties of these terpolymers are tailored by controlling the amount of a methyl methacrylate stiff monomer versus a similar monomer containing flexible poly(ethylene glycol) chains. Dopamine methacrylamide, the cross‐linking monomer, is a catechol moiety analogous to 3,4‐dihydroxyphenylalanine, a key component in the adhesive proteins of marine mussels. Bulk adhesion of this family of terpolymers is tested on metal and plastic substrates. Incorporating higher amounts of poly(ethylene glycol) into the terpolymer introduces flexibility and ductility. By taking a systematic approach to polymer design, the region in which material strength and ductility are balanced in relation to the substrate modulus is found, thereby yielding the most robust joints.     

Design criterion for fatigue strengthening of riveted beams in a 120-year-old railway metallic bridge using pre-stressed CFRP plates

This study presents a design criterion developed for fatigue strengthening of a 120-year-old metallic railway bridge in Switzerland and presents a pre-stressed un-bonded reinforcement (PUR) system developed to apply the strengthening. The PUR system uses carbon fiber reinforced polymer (CFRP) plates; however, unlike conventional pre-stressed CFRP reinforcement methods, preparation of the existing metallic bridge surface is not required. This decreases the time required for on-site strengthening procedures. The principle of the constant life diagram (CLD) and two fatigue failure criteria (Johnson and Goodman) are described. Analytical formulations are developed based on the CLD method to determine the minimum CFRP pre-stress level required to prevent fatigue crack initiation. The PUR system uses an applied pre-stress force to reduce the mean stress level (and stress ratio) to shift an existing fatigue-susceptible metallic detail from the ‘at risk’ finite life regime to the ‘safe’ infinite life regime. The applied CLD method is particularly valuable when the stress history of the detail is not known and it is difficult to assess the remaining fatigue life. Moreover, it is shown that the currently adopted approach in many structural codes which emphasizes stress range as the dominant parameter influencing fatigue life are non-conservative for tension–tension stress patterns (i.e., stress ratios of 0 < R < 1). Analyses show that the modified Johnson formula accurately reflects the combined effect of stress range, mean stress level, and material properties, and offers a relatively easy design procedure. Details of a retrofit field application on members of a riveted wrought iron railway bridge are given. A wireless sensor network (WSN) system is used for long-term monitoring of the on-site CFRP stress levels and temperature of the retrofitted details. WSN measurements indicate that increases in ambient temperature result in increased CFRP pre-stress levels.     

Triphenylphosphonium (TPP)-Based Antioxidants: A New Perspective on Antioxidant Design

Mitochondrial oxidative damage and dysfunction contribute to a wide range of human diseases. Considering the limitation of conventional antioxidants and that mitochondria are the main source of reactive oxygen species (ROS) which induce oxidative damage, mitochondria-targeted antioxidants which can selectively block mitochondrial oxidative damage and prevent various types of cell death have been widely developed. As a lipophilic cation, triphenylphosphonium (TPP) has been commonly used in designing mitochondria-targeted antioxidants. Conjugated with the TPP moiety, antioxidants can achieve more than 1000-fold higher mitochondrial concentration depending on cell membrane potentials and mitochondrial membrane potentials. Herein we discuss the deficiencies of conventional antioxidants and the advantages of mitochondrial targeting, and review various types of TPP-based mitochondria-targeted antioxidants. These provide theoretical and background support for the design of new anti-oxidant.     

Effect of hyperbranched poly(citric polyethylene glycol) with various polyethylene glycol chain lengths on starch plasticization and retrogradation

A series of hyperbranched poly(citric polyethylene glycol) (PCPEG) materials with varied polyethylene glycol (PEG) chain lengths as plasticizers were mixed with maize starch (MS) via cooking and film‐forming. The structure, pasting property, plasticization, aging property, moisture absorption and compatibility of plasticized starches were studied by means of Fourier transform infrared spectroscopy, X‐ray diffraction, rapid viscosity analysis, tension testing, moisture absorption measurements and scanning electron microscopy. Compared with PEG and citric acid, PCPEG was more effective in promoting starch chain movement and inhibiting the retrogradation of starch film. Also, PCPEG/MS had smaller moisture content. The longer the plasticizer chain, the better were the aging resistance and moisture resistance of starch. But with an increase of PEG chain length, mechanical properties of PCPEG/MS deteriorated and the compatibility between PCPEG and MS decreased. The hyperbranched derivative of PEG with longer chain exhibited improved plasticization and compatibility with starch. © 2019 Society of Chemical Industry     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry