Thermotropic liquid crystalline polymers as protective coatings for aerospace

Liquid crystalline polymers (LCPs) have potential as multifunctional, environmentally friendly coatings for aerospace, overcoming the disadvantages of current materials. Their use, however, has been hindered mainly by their poor adhesion strength. The present work studies novel liquid crystalline thermosetting polymers (LCTs), which can overcome the disadvantages of commercial LCPs for protective coatings in aerospace applications. Phenylethynyl terminated liquid crystalline oligomers based on 4-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA) were synthesized and melt-pressed on grit-blasted aluminum to obtain 25 μm and 80 μm thick coatings. The presence of coating defects and curing kinetics were investigated, and the adhesion, mechanical properties and environmental resistance were compared with a commercial LCP reference material (Vectra^®). The LCTs showed highly improved adhesion; moreover, fully cured LCTs are harder and stiffer than commercial LCPs, which are expected to increase their wear and impact resistance. The coatings showed no swelling, peeling, or blistering after 500 h of full immersion in fluids such as jet fuel and turbine oil; furthermore, LCTs resisted 1000 h in corrosive fog (salt-spray) and hot moisture. Exposed samples retained their hardness, modulus, and pull-off strength, evidencing the outstanding chemical resistance of these LCTs. Our findings showed the potential of LCTs as protective and wear resistant coatings, particularly in the aggressive environments of aerospace applications. However, results suggest that exposed coating/substrate interfaces constitute paths for environmental attack. Further research aims at elucidating the possible mechanisms.     

Novel Type II Fatty Acid Biosynthesis (FAS II) Inhibitors as Multistage Antimalarial Agents

Malaria is a potentially fatal disease caused by Plasmodium parasites and poses a major medical risk in large parts of the world. The development of new, affordable antimalarial drugs is of vital importance as there are increasing reports of resistance to the currently available therapeutics. In addition, most of the current drugs used for chemoprophylaxis merely act on parasites already replicating in the blood. At this point, a patient might already be suffering from the symptoms associated with the disease and could additionally be infectious to an Anopheles mosquito. These insects act as a vector, subsequently spreading the disease to other humans. In order to cure not only malaria but prevent transmission as well, a drug must target both the blood‐ and pre‐erythrocytic liver stages of the parasite. P. falciparum (Pf) enoyl acyl carrier protein (ACP) reductase (ENR) is a key enzyme of plasmodial type II fatty acid biosynthesis (FAS II). It has been shown to be essential for liver‐stage development of Plasmodium berghei and is therefore qualified as a target for true causal chemoprophylaxis. Using virtual screening based on two crystal structures of PfENR, we identified a structurally novel class of FAS inhibitors. Subsequent chemical optimization yielded two compounds that are effective against multiple stages of the malaria parasite. These two most promising derivatives were found to inhibit blood‐stage parasite growth with IC₅₀ values of 1.7 and 3.0 μM and lead to a more prominent developmental attenuation of liver‐stage parasites than the gold‐standard drug, primaquine.     

A simple strategy to generate light-responsive azobenzene-containing epoxy networks

Azobenzene containing epoxy networks are a class of photosensitive materials characterized by high thermal, optical and mechanical stability, promising for reversible optical storage applications. Here, we propose an encouraging two-step method to fabricate crosslinked coatings by simply reacting an amine-functionalized azobenzene and an epoxy resin in bulk for specified times to get soluble products (network precursors). Thin films based on these precursors were prepared, and thermally crosslinked in order to obtain high-T_g materials. The optical response of the materials was determined, both before and after crosslinking. In the case of the samples as prepared, the dynamic time response of the system is fast, as well as the relaxation of the photoinduced birefringence, as expected due to the high mobility of the chromophore. On the other hand, crosslinked systems have a slightly slower response, but higher values of remnant birefringence, providing stability of the photoinduced orientation, what makes them promising materials to use in optical storage applications. Besides, further analysis on the effect of temperature on the induced birefringence of the polymeric networks was also conducted to help optimization of material design. Finally, we had presented some preliminary investigations of surface relief grating recording in the obtained new materials.     

Deep HDS over NiMo/Zr-SBA-15 catalysts with varying MoO3 loading

In the present work, with the aim of searching for new, highly effective catalysts for deep HDS, a series of NiMo catalysts with different MoO₃ loadings (6–30 wt.%) was prepared using SBA-15 material covered with ZrO₂-monolayer as a support. Prepared catalysts were characterized by N₂ physisorption, small- and wide-angle XRD, UV–vis diffuse reflectance spectroscopy, temperature-programmed reduction, SEM-EDX and HRTEM, and their catalytic activity was evaluated in the 4,6-dimethyldibenzothiophene hydrodesulfurization (HDS). It was observed that ZrO₂ incorporation on the SBA-15 surface improves the dispersion of the Ni-promoted oxidic and sulfided Mo species, which were found to be highly dispersed, up to 18 wt.% of MoO₃ loading. Further increase in metal charge resulted in the formation of MoO₃ crystalline phase and an increase in the stacking degree of the MoS₂ particles. All NiMo catalysts supported on ZrO₂-modified SBA-15 material showed high activity in HDS of 4,6-DMDBT. The best catalyst having 18 wt.% MoO₃ and 4.5 wt.% NiO was almost twice more active than the reference NiMo/γ-Al₂O₃ catalyst. High activity of NiMo/Zr-SBA-15 catalysts and its evolution with metal loading was related to the morphological characteristics of the MoS₂ active phase determined by HRTEM.     

Comparison of Oxidation Stability and Quenchant Cooling Curve Performance of Soybean Oil and Palm Oil

The potential use of vegetable oil-derived industrial oils continues to be of great interest because vegetable oils are relatively non-toxic, biodegradable, and they are a renewable basestock alternative to petroleum oil. However, the fatty ester components containing conjugated double bonds of the triglyceride structure of vegetable oils typically produce considerably poorer thermal-oxidative stability than that achievable with petroleum basestocks under typical use conditions. Typically, these conditions involve furnace loads of hot steel (850 °C), which are rapidly immersed and cooled to bath temperatures of approximately 50-60 °C. This is especially true when a vegetable oil is held in an open tank with agitation and exposed to air at elevated temperatures for extended periods of time (months or years). This paper will describe the thermal-oxidative stability and quenching performance of soybean oil and palm oil and the resulting impact on the heat transfer coefficient. These results are compared to typical fully formulated, commercially available accelerated (fast) and an unaccelerated (slow) petroleum oil-based quenchants.     

Assessment of heavy metals remobilization by fractionation: comparison of leaching tests applied to roadside sediments

The pollution emitted by traffic activities and road maintenance is an area of great interest as contaminants can be transported to roadside sediments and pose a risk to environmental and human health. In the presentwork, deposited pollution in roadside sediments has been assessed by sampling along a highly traveled highway in Barcelona and the surrounding area. The available amounts of the heavy metals was determined by applying different leaching tests and calculating the concentration enrichment ratio (CER) and the environmental concentration guideline values (ECG). To gain information on the heavy metals (HMs) fractionation, the sequential extraction scheme (SES), established by the Standard Measurement and Testing (SM&T), was implemented, and the results were compared with those obtained by single leaching tests. An anthropogenic enhancement of certain metals was observed after considering both the CER and ECG values. However, if only ECG values were considered, an overestimation of the anthropogenically enhanced pollutants was obtained due to disregarding geochemical and particle size variability. CER values provide a more realistic assessment by determining different levels of anthropogenic impact. Thus, CER values suggest a minimum anthropogenic apportion for metals such as Cd, Cr, and Ni, whereas different situations from significant to extreme anthropogenic contribution were observed for Zn, Pb, and Cu. These results have been complemented by other leaching tests that minimize the time-consuming environmental evaluation. In this study, HCI extraction produces suitable results for a quick screening since they correlate well with the corresponding SES: Cu(r2 = 0.798), Pb(r2 = 0.958) and Zn(r2 = 0.901). Mild extractants have been observed to be limited to highly polluted samples due to their low leaching power. The information obtained following this procedure helps to identify hazardous areas that need a remedial strategy.     

Enhanced oil recovery by means of alkali injection. Behavior of the SARA fractions

Abstract

The presence of an alkali such as sodium hydroxide (NaOH) within a process of enhanced recovery of crude oil having certain acidity allows the formation of surfactants with the ability of enhancing the separation of the crude oil from the reservoir rock where it is adsorbed due to a change of wettability. This work focused on studying the effect of NaOH on the enhanced recovery, in terms of the SARA composition, of two different API gravity crude oils (38.5 and 24.1°) having different total acid number. The results showed the existence of acid components with high and low reactivity to NaOH in the crude oil, where the first group is responsible of the in-situ synthesis of the surfactant. Moreover, it was found that the utilization of the alkali improved the recovery of the SARA fractions for each crude oil, especially for the 24.1°API crude oil for which the recovery resulted twice or three times higher to the evaluated for the 38.5°API crude oil. Additionally, it was found that a minimum of 0.2?wt% of NaOH reduced up to 4 times the value of the interfacial tension between the crude oil and the brine, regardless of the type of crude oil.