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     

A crossover‐UNIQUAC model for critical and noncritical LLE calculations

A new model, named the crossover‐UNIQUAC model, has been proposed based on the crossover procedure for predicting constant‐pressure liquid–liquid equilibria (LLE). In this manner, critical fluctuations were incorporated into the classical UNIQUAC equation. Coexistence curves were estimated for systems having a diverse range of asymmetries. These systems included the LLE of five different mixtures, composed of nitrobenzene with one of the members of the alkane homologous family (either pentane, octane, decane, dodecane, or tetradecane), as well as an extra system having a different chemical nature, namely the mixture of n‐perfluorohexane and hexane, to further check the validity of the proposed approach. Using these nonideal mixtures, the validity of the new model was investigated within wide ranges, covering near‐critical to regions falling far away from the critical point. The graphical trends, as well as the quantitative comparison with experimental data indicated the good agreement of the proposed model results with the experimental data. A maximum AARD% value of 3.97% was obtained in calculating molar compositions by the proposed model for such challenging systems covering noncritical, as well as critical regions. In addition, to show the strength of the proposed crossover approach to describe properties other than LLE, molar heat capacities were investigated for the system of nitrobenzene + dodecane. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3094–3103, 2015     

Vitamin C Enhances Vitamin E Status and Reduces Oxidative Stress Indicators in Sea Bass Larvae Fed High DHA Microdiets

Docosahexaenoic acid (DHA) is an essential fatty acid necessary for many biochemical, cellular and physiological functions in fish. However, high dietary levels of DHA increase free radical injury in sea bass (Dicentrarchus labrax) larvae muscle, even when vitamin E (α-tocopherol, α-TOH) is increased. Therefore, the inclusion of other nutrients with complementary antioxidant functions, such as vitamin C (ascorbic acid, vitC), could further contribute to prevent these lesions. The objective of the present study was to determine the effect of vitC inclusion (3,600?mg/kg) in high DHA (5?% DW) and α-TOH (3,000?mg/kg) microdiets (diets 5/3,000 and 5/3,000?+?vitC) in comparison to a control diet (1?% DHA DW and 1,500?mg/kg of α-TOH; diet 1/1,500) on sea bass larvae growth, survival, whole body biochemical composition and thiobarbituric acid reactive substances (TBARS) content, muscle morphology, skeletal deformities and antioxidant enzymes, insulin-like growth factors (IGFs) and myosin expression (MyHC). Larvae fed diet 1/1,500 showed the best performance in terms of total length, incidence of muscular lesions and ossification degree. IGFs gene expression was elevated in 5/3,000 diet larvae, suggesting an increased muscle mitogenesis that was confirmed by the increase in the mRNA copies of MyHC. vitC effectively controlled oxidative damages in muscle, increased α-TOH larval contents and reduced TBARS content and the occurrence of skull deformities. The results of the present study showed the antioxidant synergism between vitamins E and C when high contents of DHA are included in sea bass larvae diets.     

How indirect supportive digital help during and after solving physics problems can improve problem-solving abilities

This study investigates the effectiveness of computer-delivered hints in relation to problem-solving abilities in two alternative indirect instruction schemes. In one instruction scheme, hints are available to students immediately after they are given a new problem to solve as well as after they have completed the problem. In the other scheme, hints are only available as worked out problems after students have finished their solution. The instruction schemes are supplied by means of a web-based program, Physhint, which supports the development of strategic knowledge [Pol, H. J., Harskamp, E. G., & Suhre, C. J. M. (2008). The effect of the timing of instructional support in a computer-supported problem-solving program for students in secondary physics education. Computers in Human Behavior, 24, 1156–1178]. This program supports novice problem solvers while undertaking physics problems concerned with forces by providing hints structured in accordance with Schoenfeld’s episodes [Schoenfeld, A. H. (1992). Learning to think mathematically: Problem solving, metacognition, and sense making in mathematics. In D. A. Grouws (Ed.), Handbook of research on mathematics teaching (pp. 224–270). New York: McMillan Publishing].     

Interaction between carbon dioxide and ionic liquids: Novel electrolyte candidates for safer Li-ion batteries

Ionic liquids (ILs) are typically molten salts at temperatures lower than 100 °C. Because of their thermal and electrochemical properties, they are good candidates to replace the state-of-the-art electrolytes used in today's Li-ion batteries. These commercial batteries often suffer from hazards caused by possible misuse. Elevated voltages and high temperatures usually lead to electrolyte degradation due to parasitic reactions with the electrodes leading to gas (mainly CO₂) evolution and may then eventually catch fire. Also, ILs are able to dissolve various gas molecules, making it possible to prevent a built-up of an overpressure inside the battery in case of undesired gas evolution. In this work, CO₂ storage in two different ionic liquids, i.e. PYR₁₄TFSI and [BMIm][BF4] is studied with regard to their respective Li-salt. Mixtures of ILs plus different concentrations of CO₂ were made. Phase diagrams of the pressure vs. temperature of the systems “liquid + vapour” to liquid transitions are drawn. Data points from 1.5 bar to 70 bar are collected with a Cailletet apparatus. Both of the ILs show good CO₂ dissolution ability; an increase of the temperature leads to an increase of the pressure needed to dissolve similar amounts of CO₂. The presence of a Li-salt hampers gas storage, particularly for PYR₁₄TFSI. A model based on the Langmuir adsorption theory is used to describe the solubility of the CO₂ in [BMIm][BF4]. The PYR₁₄TFSI IL does not obey the Langmuir-like solubility behaviour. Hence, the solubility then is described by the formation of discrete bonds between the CO₂ and the solvent, similarly to the concept of adspecies and surface sites.     

Identification of Thiols in Yellow Onion (Allium cepa L.) Using Solvent Vented Large Volume Injection GC‐MS

Thiols are often highly odor active molecules and as such can significantly contribute to aroma while being present at extremely low concentrations. This paper details the identification of thiols in yellow onion juice by solvent extraction followed by thiol enrichment using a mercuric agarose gel column. Due to the inherent thermal instability and low concentrations of thiols in onion, chromatographic analysis utilized larger volume solvent elimination injections. New sulfur compounds in onion included 1,1‐propanedithiol, bis‐(1‐sulfanylpropyl)‐sulfide, 1‐methylsulfanyl‐1‐propanethiol, 1‐propylsulfanyl‐1‐propanethiol, and 1‐allylsulfanyl‐1‐propanethiol. A discussion on the potential route of formation for each compound is included along with the orthonasal and retronasal evaluations of the synthesized molecules. This work investigated and identified 5 newly identified compounds present in onions that can impart onion character at low concentrations levels.     

Collapse test and moment capacity of the Ruytenschildt reinforced concrete slab bridge

A large number of existing reinforced concrete solid slab bridges in the Netherlands are found to be insufficient for shear upon assessment. However, research has shown additional sources of capacity in slab bridges, increasing their total capacity and possibly changing their failure mode. Previous testing was limited to half-scale slab specimens cast in the laboratory. To study the full structural behaviour of slab bridges, testing to failure of a bridge is necessary. Research on load testing is carried out in order to develop load testing guidelines. In August 2014, a bridge was tested in two spans. The bridge was load tested, and additional cycles until yielding occurred in the reinforcement were added to the experiment. Though calculations with current design provisions showed that the bridge could fail in shear, the field test showed failure in flexure before shear. The unity check for flexure was determined. The experiment shows that the methods for rating of existing reinforced concrete slab bridges are conservative.     

Decomposition kinetics and recycle of binary hydrogen‐tetrahydrofuran clathrate hydrate

Decomposition kinetics and recycle of hydrogen–tetrahydrofuran (H₂–THF) clathrate hydrates were investigated with a pressure decay method at temperatures from 265.1 to 273.2 K, at initial pressures from 3.1 to 8.0 MPa, and at stoichiometric THF hydrate concentrations for particle sizes between 250 and 1000 μm. The decomposition was modeled as a two‐step process consisting of H₂ diffusion in the hydrate phase and desorption from the hydrate cage. The adsorption process occurred at roughly two to three times faster than the desorption process, whereas the diffusion process during formation was slightly higher (ca. 20%) than that during decomposition. Successive formation and decomposition cycles showed that occupancy seemed to decrease only slightly with cycling and that there were no large changes in hydrate structure due to cycling. Results provide evidence that the formation and decomposition of H₂ clathrate hydrates occur reversibly and that H₂ clathrate hydrates can be recycled with pressure. © 2010 American Institute of Chemical Engineers AIChE J, 2011