Effect of structure on the properties of polyurethanes based on aromatic cardanol-based polyols prepared by thiol-ene coupling

Industrial-grade cardanol and 2-mercaptoethanol were reacted to generate hydroxyl-functionalized cardanol by UV, free-radical-initiated thiol-ene coupling between the double bond moieties of the cardanol long carbon side chain and thiol functional groups. The average hydroxyl number of the hydroxyl-functionalized cardanol was controlled by reaction time, with the hydroxyl values of this ranging within 168–201 mg KOH g⁻¹. This cardanol was then used as a polyol to prepare cardanol-based polyurethane with hexamethylene diisocyanate and a NCO/OH ratio of 1. To compare the effect of cardanol-based polyols with the properties of cardanol-based polyurethane, cardanol modified with 10-undecylenate was used as a raw material to prepare cardanol-based polyols, including the long carbon chain of 10-undecylenate. All properties were examined, and data revealed that cardanol-based polyols including this long carbon chain can improve the hydrophobic and mechanic properties of the cardanol-based polyurethane.     

Nanocrystalline transition metal oxides and their composites with reduced graphene oxide and carbon nanotubes for photocatalytic applications

Transition metal oxide nanoparticles (CuO, ZnO & Fe₂O₃) and mixed metal oxides CuO. ZnO.Fe₂O₃ were fabricated by facile co-precipitation approach for photocatalytic treatment of organic dyes. The structural features, phase purity, crystallite size and morphology of individual and mixed metal oxides were analysed by X-rays diffraction patterns (XRD) and scanning electron microscopic (SEM) analysis. Electrical behaviour of CuO, ZnO, Fe₂O₃ and mixed metal oxides CuO. ZnO.Fe₂O₃ was explored by current-voltage (I-V) measurements. Functional groups present in the synthesized metal oxides were investigated by Fourier transform infrared spectroscopy (FTIR) which ensures the existence of M-O functional groups in the samples. The optical bandgap analysis was carried out by UV–visible spectroscopic technique which revealed that the blend of three different transition metal oxides reduced the bandgap energy of mixed metal oxides. The reason behind this reduced bandgap energy is formation of new electronic state which arises due to the metal-oxygen interactions. Moreover, the nanocomposites of CuO.ZnO.Fe₂O₃ with reduced graphene oxide (rGO) and carbon nanotubes (CNTs) were prepared to study the effect of the carbonaceous materials on the rate of photodegradation. These carbonaceous nanomaterials have plethora properties which can bring advancement in sector of photocatalytic treatment of wastewater. The photocatalytic experiments were performed using methylene blue (MB) as standard dye for comparative study of metal oxides and their composites with rGO and CNTs. The percentage degradation of methylene blue (MB) by nanocomposite CuO.ZnO.Fe₂O₃/rGO is 87% which is prominent among all samples. This result ascribed the photocatalytic aspects of reduced graphene oxide along with mixed metal oxides.     

Alkali catalyzed liquefaction of corncob in supercritical ethanol–water

Corncob liquefaction in supercritical ethanol–water was performed with and without the addition of an alkali catalyst by direct addition or biomass impregnation in a 250-cm³ batch reactor. The effects of temperature, solvent and alkali addition on the biomass conversion level and oil yield were investigated to find the optimum condition. For non-catalytic liquefaction using a 1:1 (v/v) ethanol: water ratio, a maximum oil yield and conversion level of 49.0% and 93.4%, respectively, were obtained at 340 °C. For alkali catalytic liquefaction, the oil yield with KOH addition (57.5%) was higher than that from KOH-impregnated corncob liquefaction (43.3%). The oil from liquefaction with KOH addition had higher heating value (26.7–35.3 MJ kg⁻¹) than the corncob (19.1 MJ kg⁻¹). The dominant components of the obtained oil were found by GC/MS analysis to be aldehyde, ester, phenol derivatives and aromatic compounds.     

Robust Superhydrophobic Fabric for Durability,Self-Cleaning,and Oil/Water Separation via Thiol–Acrylate Polymerization

In recent years, highly efficient oil/water separation materials have brought much attention. It requests superhydrophobic surfaces with a rapid and facile separation process, excellent durability, and large-scale fabrication. Herein, a facile vapor-liquid sol-gel, and free radical polymerization reaction method to prepare the durable and robust superhydrophobic cotton fabric is proposed. Moreover, the fabric can be used for highly efficient and various oil/water separation. It is prepared via a simple two-step process, including a vapor-liquid sol-gel process to deposit with thiols particles, and then followed a free radical polymerization reaction to graft 2,2,3,4,4,4-hexafluorobutyl methacrylate. Scanning electron microscopy and Fourier transform infrared spectrometry prove that the rough structures are generated from the hydrolysis condensation reaction between tetraethyl orthosilicate and 3-mercaptopropyltriethoxysilane. As a result, the synthetic chemical composition provided by the natural fabric and silica nanoparticles synergistically construct a superhydrophobic surface with water contact angles and shedding angle of 158° and 9°, respectively. Additionally, the treated fabric exhibits excellent chemical resistance and self-cleaning ability. Remarkably, the fabric still retains superhydrophobic and excellent mechanical robustness after 30 cycles of various oil/water separation. In summary, the resultant fabrics with excellent chemical resistance, remarkable mechanical robustness, and versatile separation abilities have potential applications in various oil/water separations.     

Improving the economics of biodiesel production through the use of low value lipids as feedstocks: vegetable oil soapstock

Semirefined and refined vegetable oils are the predominant feedstocks for the production of biodiesel. However, their relatively high costs render the resulting fuels unable to compete with petroleum-derived fuel. We have investigated the production of fatty acid methyl esters (FAME; biodiesel) from soapstock (SS), a byproduct of edible oil refining that is substantially less expensive than edible-grade refined oils. Multiple approaches were taken in search of a route to the production of fatty acid methyl esters from soybean soapstock. The most effective method involved the complete saponification of the soapstock followed by acidulation using methods similar to those presently employed in industry. This resulted in an acid oil with a free fatty acid (FFA) content greater than 90%. These fatty acids were efficiently converted to methyl esters by acid-catalyzed esterification. The fatty acid composition of the resulting ester product reflected that of soy soapstock and was largely similar to that of soybean oil. Following a simple washing protocol, this preparation met the established specifications for biodiesel of the American Society for Testing and Materials. Engine emissions and performance during operation on soy soapstock biodiesel were comparable to those on biodiesel from soy oil. An economic analysis suggested that the production cost of soapstock biodiesel would be approximately US$ 0.41/l, a 25% reduction relative to the estimated cost of biodiesel produced from soy oil.     

Bioelectrochemical sulfate reduction enhanced nitrogen removal from industrial wastewater containing ammonia and sulfate

Low organic carbon-to-nitrogen ratio and existing sulfate (SO₄²⁻) in industrial wastewater limited nitrogen removal. Coupling SO₄²⁻ reduction with sulfide autotrophic denitrification provides a novel strategy. Herein, bioelectrochemical sulfate reduction was coupled with heterotrophic sulfate reduction to drive sulfide autotrophic denitrification. In this coupled system, total nitrogen (TN) removal efficiency was increased from ~25% to ~85% by inputting −45 mA electricity. With the help of supplying electrons to denitrification through SO₄²⁻ reduction, coulomb efficiency was improved to 61.5%. Also, bioelectrochemical sulfate reduction could improve sulfur recovery and thus increase TN removal efficiency. Furthermore, through tuning turnover numbers of SO₄²⁻, high TN removal efficiency can be obtained at various concentrations of SO₄²⁻. Moreover, main functional bacteria in this system were identified. Finally, ~75% TN removal efficiency was achieved with real wastewater in this system. Overall, this work offered a new approach for efficient nitrogen removal from industrial wastewater containing SO₄²⁻.     

Ultrahigh molecular weight polyethylene with improved crosslink density,oxidation stability,and microbial inhibition by chemical crosslinking and tea polyphenols for total joint replacements

Highly crosslinked ultrahigh molecular weight polyethylene (UHMWPE) stabilized by vitamin E (VE) is widely applied in artificial joints as the bearings. Despite the approval, there is a discord that VE lowers the crosslinking efficiency, limiting its use at high concentration. In this work, we aim to obtain highly crosslinked and oxidation resistant UHMWPE through the conjunction of tea polyphenol and chemical crosslinking. We hypothesized that highly incorporated tea polyphenol with multiple reactive sites can ameliorate crosslinking efficiency of chemical crosslinked UHMWPE in comparison to VE. Epigallocatechin gallate (EGCG) as representative tea polyphenol was incorporated into UHMWPE at high concentration (2–8 wt%), followed by chemical crosslinking with 2 wt% organic peroxide. Unlike VE/UHMWPE blends as the control, chemical crosslinking achieved an increasing trend in crosslink density of EGCG/UHMWPE blends with increasing antioxidant concentration. High concentration of EGCG also enhanced the oxidation stability of UHMWPE. Intriguingly, EGCG endowed UHMWPE with an excellent antimicrobial property, which was inefficient in VE/UHMWPE. Cell viability was hardly affected by the high loaded antioxidant and peroxide. The chemically crosslinked UHMWPE blended with EGCG is proved to be a reasonable, cost effective and realistic alternative for use in artificial joints.     

Fabrication of phytic acid embellished kaolinite and its effect on the flame retardancy and thermal stability of ethylene vinyl acetate composites

A modified kaolinite by grafting with phytic acid (PA-g-Kaol) is fabricated, and it was introduced into ethylene vinyl acetate (EVA) with intumescent flame retardancy (IFR) together to improve the flame retardancy of EVA composites. The results show the limiting oxygen index value of EVA/ (18.0 wt% IFR)/ (2.0 wt% PA-g-Kaol) is 30.8%. Meanwhile, there is only one dripping produced in the vertical burning test. What's more, the flame-retardant mechanism is demonstrated by TG-IR, real-time-IR and GC–MS analysis. The results indicate that some pyrolytic products of IFR and PA-g-Kaol, like ammonia and phosphoric acid, catalyze the crosslinking of EVA and flame retardant, the resultant compact char protects the substrate from further burning.     

Effects of the molecular structure from pitch fractions on the properties of pitch-based electrospun nanofibers

Mesophase pitch was separated into different pitch fractions to investigate the effect of pitch fractions on the properties of their nanofibers prepared by electrospinning. The evolution of different pitch fractions-derived nanofibers during stabilization and carbonization were explored, and the properties of the resultant carbon nanofibers (CNFs) as electrode materials for supercapacitor were compared. Results indicated that the hexane insoluble-toluene soluble (HI-TS) and toluene insoluble-tetrahydrofuran (THF) soluble (TI-THFS) fractions had good spinnability due to their narrow molecular weight distribution. Moreover, compared with HI-TS and THF insoluble (THFI), TI-THFS consisted of appropriate aromaticity and branched alkyl groups which promoted the stabilization and carbonization behaviors of its nanofibers, resulting in maintaining ideal fiber morphology of TI-THFS-derived nanofiber due to the mitigation of their exothermic reactions. Meanwhile, the TI-THFS-derived CNFs presented the highest surface area of 543 m² g⁻¹ and exhibited an excellent specific capacitance of 167 F g⁻¹ at 0.5 A g⁻¹ in 6 M KOH electrolyte.     

Improving classification-based diagnosis of batch processes through data selection and appropriate pretreatment

This work considers the application of classification algorithms for data-driven fault diagnosis of batch processes. A novel data selection methodology is proposed which enables online classification of detected disturbances without requiring the estimation of unknown (future) process behavior, as is the case in previously reported approaches.The proposed method is benchmarked in two case studies using the Pensim process model of Birol et al. (2002) implemented in RAYMOND. Both a simple k Nearest Neighbors (k-NN) and complex Least Squares Support Vector Machine (LS-SVM) are employed for classification to demonstrate the generic nature of the proposed approach. In addition, the influence of different data pretreatment methods on the classification performance is discussed, together with a motivation for selecting the correct pretreatment steps. Finally, the influence of the number of available training batches is studied.The results demonstrate that a good classification performance can be achieved with the proposed data selection method even with a low number of faulty training batches by exploiting knowledge on the nature of the to-be-diagnosed faults in the data pretreatment. This provides a proof of concept for classification-based batch diagnosis and demonstrates the importance of incorporating process insight in the construction of data-driven process monitoring and diagnosis tools.