Fully renewable limonene‐derived polycarbonate as a high‐performance alkyd resin

Limonene‐derived polycarbonate‐based alkyd resins (ARs) have been prepared by copolymerization of limonene dioxide with CO₂, catalysed by a β‐diiminate zinc–bis(trimethylsilyl)amido complex, and subsequent chemical modification with soybean oil fatty acids using triphenylethylphosphonium bromide as the catalyst. This quantitative partial modification was realized via epoxy–carboxylic acid chemistry, affording ARs with higher oil lengths, lower polydispersities and higher glass transition temperatures (T_g) in comparison to a conventional polyester AR based on phthalic acid, multifunctional polyol pentaerythritol and soybean fatty acid. The novel limonene polycarbonate AR and the conventional polyester AR were evaluated as coatings and both the physical drying (without the presence of the oxidative drying accelerator Borchi® Oxy Coat) and chemical curing (with Borchi® Oxy Coat) processes of these coatings were monitored by measuring the König hardness and complex modulus development with time. A better performance was obtained for the alkyd paint containing polycarbonates modified with fatty acids (FA‐PCs), which showed a faster chemical drying, a higher König hardness and a higher T_g in coating evaluation, demonstrating that the fully renewable FA‐PCs are promising resins for alkyd paint applications. © 2019 Society of Chemical Industry     

Reactivity,Selectivity, and Stability of Zeolite-Based Catalysts for Methane Dehydroaromatization

Non-oxidative dehydroaromatization is arguably the most promising process for the direct upgrading of cheap and abundant methane to liquid hydrocarbons. This reaction has not been commercialized yet because of the suboptimal activity and swift deactivation of benchmark Mo-zeolite catalysts. This progress report represents an elaboration on the recent developments in understanding of zeolite-based catalytic materials for high-temperature non-oxidative dehydroaromatization of methane. It is specifically focused on recent studies, relevant to the materials chemistry and elucidating i) the structure of active species in working catalysts; ii) the complex molecular pathways underlying the mechanism of selective conversion of methane to benzene; iii) structure, evolution and role of coke species; and iv) process intensification strategies to improve the deactivation resistance and overall performance of the catalysts. Finally, unsolved challenges in this field of research are outlined and an outlook is provided on promising directions toward improving the activity, stability, and selectivity of methane dehydroaromatization catalysts.     

Robust optimisation of sustainable food grain transportation with uncertain supply and intentional disruptions

The proliferating need for sustainability intervention in food grain transportation planning is anchoring the attention of researchers in the interests of stakeholders and environment at large. Uncertainty associated with food grain supply further intensifies the problem steering the need for designing robust, cost-efficient and sustainable models. In line with this, this paper aims to develop a robust and sustainable intermodal transportation model to facilitate single type of food grain commodity shipments while considering procurement uncertainty, greenhouse gas emissions, and intentional hub disruption. The problem is designed as a mixed integer non-linear robust optimisation model on a hub and spoke network for evaluating near optimal shipment quantity, route selection and hub location decisions. The robust optimisation approach considers minimisation of total relative regret associated with total cost subject to several real-time constraints. A version of Particle Swarm Optimisation with Differential Evolution is proposed to tackle the resulting NP-hard problem. The model is tested with two other state-of the art meta-heuristics for small, medium, and large datasets subject to different procurement scenarios inspired from real time food grain operations in Indian context. Finally, the solution is evaluated with respect to total cost, model and solution robustness for all instances.     

Characterization of superficial modification of ferrous rusted substrates subjected to dechlorination-electrochemical process

Preservation of archaeological artefacts after their removal from saline media is a difficult task due to the chloride content of the oxide layers which are unstable in atmospheric conditions, especially if the relative humidity exceeds 85%. For this reason, removal of chlorides from rust layers is one of the priorities of conservationists or restorers of historical artefacts. However, removal of chloride ions is not an easy procedure because of the many considerations involved in the process. In this research, artificially pre-rusted iron samples and an actual historical cannonball were subject to a dechlorination process in a potassium hydroxide solution to measure constant chloride release in a bulk solution. After the chloride removal process, a commercial protective layer was applied to the rust for stabilization purposes. It was calculated that the kinetics of the dechlorination process is driven by diffusion behaviour following Fick’s second law. When this diffusion process prevails, the dechlorination extraction affects the integrity of rust layers as is demonstrated with scanning electron microscopy and X-ray diffraction analyses. It was proven that the chloride removal procedure causes the studied iron layers to stiffen, provoking superficial modification and, in some cases, fractures of the rust. By means of electrochemical impedance spectroscopy it was calculated that the magnitude of the positive effect of the dechlorinated samples depends on the protective features of the rust. Therefore, this research reveals that an efficient chloride removal procedure depends on the electrochemical properties of the dechlorination process and the initial morphology of the iron rust.     

Crashworthiness characteristics of natural ramie/bio-epoxy composite tubes for energy absorption application

Using metallic materials in automotive structures increases weight, fuel consumption and cost, therefore, certain trends have begun to use lightweight and cheaper materials. Fibre composites are used in automotive applications because they are stiff, lightweight and stronger than bulk material, as well as they have a comparable energy-absorbing capacity to that of metallic materials. The aim of this study is to investigate the potentials in natural ramie/bio-epoxy composite in crash energy absorption applications. Cubic specimens consisted of 12, 24 and 30 plies of ramie/bio-epoxy laminates with 50, 80 and 120 mm long which were prepared by hand layup method. Static axial compression load was then applied and the energy-absorbing capability of the ramie/epoxy composite was evaluated. The crashworthiness characteristics of the composite tubes were evaluated by measuring the average and peak crushing load, specific energy absorption, total absorbed energy and crush force efficiency in quasi-static axial compression. The failure mode and behaviour of the tubes were investigated by taking photographs and recording the load–displacement curves during the test accomplishment. The test results indicated that natural ramie/bio-epoxy composite tube has the great potential to be used as an effective energy-absorbing device.     

Oxygenated VOCs,aqueous chemistry,and potential impacts on residential indoor air composition

Dampness affects a substantial percentage of homes and is associated with increased risk of respiratory ailments; yet, the effects of dampness on indoor chemistry are largely unknown. We hypothesize that the presence of water‐soluble gases and their aqueous processing alters the chemical composition of indoor air and thereby affects inhalation and dermal exposures in damp homes. Herein, we use the existing literature and new measurements to examine the plausibility of this hypothesis, summarize existing evidence, and identify key knowledge gaps. While measurements of indoor volatile organic compounds (VOCs) are abundant, measurements of water‐soluble organic gases (WSOGs) are not. We found that concentrations of total WSOGs were, on average, 15 times higher inside homes than immediately outside (N = 13). We provide insights into WSOG compounds likely to be present indoors using peer‐reviewed literature and insights from atmospheric chemistry. Finally, we discuss types of aqueous chemistry that may occur on indoor surfaces and speculate how this chemistry could affect indoor exposures. Liquid water quantities, identities of water‐soluble compounds, the dominant chemistry, and fate of aqueous products are poorly understood. These limitations hamper our ability to determine the effects of aqueous indoor chemistry on dermal and inhalation exposures in damp homes.