Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase

We characterized the stationary points along the nucleophilic substitution (SN2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M− + CH3X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > SN2 > OI. The OI channel that results in oxidative insertion complex [CH3–M–X]− is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a SN2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M− to Pd, a d10 metal, because the symmetry of their HOMO orbital is different. The back-side attack SN2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invSN2-TS’s are, in general, submerged. The shape of this M− + CH3X SN2 PES is flatter as compared to that of a main-group base like F− + CH3X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH3−X∙··M]− can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH3 + MX− through halogen abstraction or bends the C-X-M angle to continue the back-side SN2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH3–M–X]−, whereas a noncovalent M–X halogen-bond interaction exists for the [CH3–X∙··M]− complex. This work explores competing channels of the M− + CH3X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions.

A Thermopile Detector Based on Micro-Bridges for Heat Transfer

A thermopile detector with their thermocouples distributed in micro-bridges is designed and investigated in this work. The thermopile detector consists of 16 pairs of n-poly-Si/p-poly-Si thermocouples, which are fabricated using a low-cost, high-throughput CMOS process. The micro-bridges are realized by forming micro trenches at the front side first and then releasing the silicon substrate at the back side. Compared with a thermopile device using a continuous membrane, the micro-bridge-based one can achieve an improvement of the output voltage by 13.8% due to a higher temperature difference between the hot and cold junctions as there is a decrease in thermal conduction loss in the partially hollowed structure. This technique provides an effective way for developing high-performance thermopile detectors and other thermal devices.

The Polysemy and Hyponymy of Mandarin Spatial Prepositions and Localisers: Building Semantic Maps from the Ground up

The goal of this paper is to offer an overview of polysemy patterns in Mandarin’s chief spatial categories: prepositions (e.g., zai) and simple and compound localisers (respectively, qian and qian-mian). The paper presents data from an elicitation study that shows how speakers can access multiple senses and hyponymy relations for the vocabulary items belonging to these categories. The paper shows that while prepositions can potentially cover different spatial relations in the opportune context (e.g., zai “at”), localisers select increasingly specific senses (e.g., qian “front” and qian-mian “front side”). The paper also shows how speakers can access hyponym-like sense relations emerging from these patterns (e.g., qian-bian covering a more specific sense than qian). Semantic dimensions such as “distance” and “location type” determine the strength of these hyponymy relations. The paper offers an account of these data based on the “semantics maps” model, which captures polysemy and hyponymy patterns via the clusters of locations they refer to. It is shown that this novel model is consistent with previous works on the polysemy of spatial categories and sheds light on how Mandarin offers a unique organisation of this domain.

Beacon-Based Individualized Hazard Alarm System for Construction Sites: An Experimental Study on Sensor Deployment

Researchers have proposed several forms of beacon sensor-based hazard alarm systems for increasing construction workers’ awareness of site hazards, but research on how to deploy beacon sensors so that the system is adequate for achieving timely individualized hazard alarms is scarce. Against this background, this research investigates the impact of different beacon sensor locations in a construction site on how quickly a worker can receive the individualized hazard alarms. This research took an experimental study approach to address this objective. After a prototype of a beacon-based hazard alarm system was developed, the system was tested in a concrete structure building under construction. In the experiment, the locations where the experimenter received the first hazard alarm were recorded in repetitive trials while the beacon sensor was located in four different locations, such as (1) at the entrance of the room, (2) behind the front side wall, (3) on the internal wall facing the access point, and (4) on the internal wall not facing the access point and in a partially enclosed room in the concrete structure. The rate of successful alarm notification (i.e., the rate that the person received the hazard alarm before arriving at the target location) was 89%, 68%, 48%, and 19%, respectively, for the four locations of the beacon sensor. Meanwhile, the heat maps indicating where the hazard alarm notification was received show that the “behind the front side wall” setting yielded the most desired pattern of notification reception, wherein the person received the hazard alarm just before arriving at the room. These results show that the hazard alarm function of the system could be severely affected by the beacon sensor’s location and implies that the locations of beacon sensors should be decided carefully based on the type of hazard involved and the workers targeted for receiving the alarms.

Review on the Sources of Power Loss in Monofacial and Bifacial Photovoltaic Technologies

An evaluation of the degradation effects on photovoltaic modules is essential to minimise uncertainties in the system operation. Bifacial photovoltaic technology is attracting attention due to the capacity of generating energy from the front and rear sides. This paper presents a review of degradation factors, for both conventional monofacial and bifacial photovoltaic modules, to highlight how the current and voltage characteristics of these technologies are affected by degradation. Microcracking, encapsulant discoloration, and light induced degradation seem to have similar effects on both modules. Contrarily, bifacial modules are more prone to potential induced degradation as the electromagnetic shielding is affected by the bifaciality. Bifacial devices are less affected by light and elevated temperature induced degradation. The degradation (1.3%) is similar for both technologies, up to 40 kWh/m2 of solar radiation. Above this value, monofacial degradation increases faster, reaching values of 7%. For tilted systems, the front side soiling degradation of 0.30% per day is similar for both technologies. For vertical systems, soiling loss for bifacial is considerably lower with values of 0.02% per day.

Synergistic Effect of Screen-Printed Single-Walled Carbon Nanotubes and Phosphorylated Cellulose Nanofibrils on Thermophysiological Comfort, Thermal/UV Resistance, Mechanical and Electroconductive Properties of Flame-Retardant Fabric

Single-walled carbon nanotubes (SWCNTs) and phosphorylated nanocellulose fibrils (PCNFs) were used as functional screen-print coatings on flame-retardant (FR) fabric, to improve its thermal resistance and thermophysiological comfort (wetting, water vapour and heat transmission) properties, while inducing it with electrical conductivity and UV protection. The effect of PCNF printing, followed by applying a hydrophobic polyacrylate (AP), on the same (back/B, turned outwards) or other (front/F, turned towards skin) side of the fabric, with and without the addition of 0.1–0.4 wt% SWCNTs, was studied by determining the amount of applied coating and its distribution (microscopic imaging), and measuring the fabric’s colour, air permeability, thickness, mechanical, flame and abrasion resistance properties. Due to the synergistic effect of PCNF and SWCNTs, both-sided printed fabric (front-side printed with PCNF and back-side with SWCNTs within AP) resulted in an increased heat transfer (25%) and an improved thermal resistance (shift of degradation temperature by up to 18 °C towards a higher value) and UV protection (UPF of 109) without changing the colour of the fabric. Such treatment also affected the moisture management properties with an increased water-vapour transfer (17%), reduced water uptake (39%) and asymmetric wettability due to the hydrophilic front (Contact Angle 46°) and hydrophobic back (129°) side. The increased tensile (16%) and tear (39%) strengths were also assessed in the warp direction, without worsening the abrasion resistance of the front-side. A pressure-sensing electrical conductivity (up to 4.9∙10−4 S/cm with an increase to 12.0∙10−4 S/cm at 2 bars) of the SWCNT-printed side ranks the fabric among the antistatic, electrostatic discharge (ESD) or electromagnetic interference (EMI) shielding protectives.