Composites Chitosan/SBA-15 with sulfonic acid as heterogeneous catalysts for biodiesel production

Free fatty acids (palmitic, stearic and oleic acid) were converted into biodiesel with methanol over composites catalysts consisting in SBA-15 with sulfonic acid groups (SBA-15-SO3H) immobilized in Chitosan (CH), at 60ºC. It was observed that the catalytic activity increased with the amount of SBA-15-SO3H dispersed in CH. It was also observed that the catalytic activity decreased in the series: palmitic acid > stearic acid > oleic. The catalytic stability of [SBA-15-SO3H]3/CH composites was studied. A good stability was observed.

Effect of temperature and moisture on high pressure lipid/oil extraction from microalgae

Commercially viable carbon–neutral biodiesel production from microalgae has potential for replacing depleting petroleum diesel. The process of biodiesel production from microalgae involves harvesting, drying and extraction of lipids which are energy- and cost-intensive processes. The development of effective large-scale lipid extraction processes which overcome the complexity of microalgae cell structure is considered one of the most vital requirements for commercial production. Thus the aim of this work was to investigate suitable extraction methods with optimised conditions to progress opportunities for sustainable microalgal biodiesel production. In this study, the green microalgal species consortium, Tarong polyculture was used to investigate lipid extraction with hexane (solvent) under high pressure and variable temperature and biomass moisture conditions using an Accelerated Solvent Extraction (ASE) method. The performance of high pressure solvent extraction was examined over a range of different process and sample conditions (dry biomass to water ratios (DBWRs): 100%, 75%, 50% and 25% and temperatures from 70 to 120 ºC, process time 5–15 min). Maximum total lipid yields were achieved at 50% and 75% sample dryness at temperatures of 90–120 ºC. We show that individual fatty acids (Palmitic acid C16:0; Stearic acid C18:0; Oleic acid C18:1; Linolenic acid C18:3) extraction optima are influenced by temperature and sample dryness, consequently affecting microalgal biodiesel quality parameters. Higher heating values and kinematic viscosity were compliant with biodiesel quality standards under all extraction conditions used. Our results indicate that biodiesel quality can be positively manipulated by selecting process extraction conditions that favour extraction of saturated and mono-unsaturated fatty acids over optimal extraction conditions for polyunsaturated fatty acids, yielding positive effects on cetane number and iodine values. Exceeding biodiesel standards for these two parameters opens blending opportunities with biodiesels that fall outside the minimal cetane and maximal iodine values.

Frictional response of fatty acids on steel

Self-assembled monolayers of fatty acids were formed on stainless steel by room-temperature solution deposition. The acids are covalently bound to the Surface as carboxylate in a bidentate manner. To explore the effect Of Saturation in the carbon backbone on friction in sliding tribology, we Study the response of saturated stearic acid (SA) and unsaturated linoleic acid (LA) as self-assembled monolayers using lateral force microscopy and nanotribometry and when the molecules are dispersed in hexadecane, using pin-on-disc tribometry. Over a very wide range (10 MPa-2.5 GPa) of contact pressures it is consistently demonstrated that the unsaturated linoleic acid molecules yield friction which is significantly lower than that of the saturated stearic acid. it is argued, using density functional theory predictions and XPS of slid track, that when the molecular backbone of unsaturated fatty acids are tilted and pressed strongly by a probe, in tribological contact, the high charge density of the double bond region of the backbone allows coupling with the steel Substrate. The interaction yields a low friction carboxylate soap film on the substrate. The saturated fatty acid does not show this effect.

Polychaete-assisted sand filters – prawn farm wastewater remediation trial

Medium bedding sand which is commonly available in coastal sedimentary deposits, and a marine polychaete-worm species from Moreton Bay recently classified as Perinereis helleri (Nereididae), were deployed in a simple low-maintenance sand filter design that potentially has application at large scale. Previous work had shown that this physical and biological combination can provide a new option for saline wastewater treatment, since the worms help to prevent sand filter blocking with organic debris and offer a profitable by-product. To test the application of this new concept in a commercial environment, six 1.84 m2 Polychaete-assisted sand filters were experimentally tested for their ability to treat wastewater from a semi-intensive prawn culture pond. Polychaetes produced exclusively on the waste nutrients that collected in these gravity-driven sand filters were assessed for their production levels and nutritional contents. Water parameters studied included temperature, salinity, pH, dissolved oxygen (DO), oxidation/ reduction potential (redox), suspended solids, chlorophyll a, biological oxygen demand (BOD), and common forms of nitrogen and phosphorus. Pond water which had percolated through the sand bed had significantly lower pH, DO and redox levels compared with inflow water. Suspended solids and chlorophyll a levels were consistently more than halved by the process. Reductions in BOD appeared dependant on regular subsurface flows. Only marginal reductions in total nitrogen and phosphorus were documented, but their forms were altered in a potentially useful way: dissolved forms (ammonia and orthophosphate) were generated by the process, and this remineralisation also seemed to be accentuated by intermittent flow patterns. Flow rates of approximately 1,500 L m-2 d-1 were achieved suggesting that a 1 ha polychaete bed of this nature could similarly treat the discharge from a 10 ha semi-intensive prawn farm. Sixteen weeks after stocking sand beds with one-month-old P. helleri, over 3.6 kg of polychaete biomass (wet weight) was recovered from the trial. Production on a sand bed area basis was 328 g m-2. Similar (P>0.05) overall biomass production was found for the two stocking densities tested (2000 and 6000 m-2; n = 3), but survival was lower and more worms were graded as small (<0.6 g) when produced at the higher density (28.2 ± 1.5 % and approx. 88 %, respectively) compared with the lower density (46.8 ± 4.4 % and approx. 76 %, respectively). When considered on a weight for weight basis, about half of the worm biomass produced was generally suitable for use as bait. The nutritional contents of the worms harvested were analysed for different stocking densities and graded sizes. These factors did not significantly affect their percentages of dry matter (DM) (18.23 ± 0.57 %), ash (19.77 ± 0.80 % of DM) or gross energy 19.39 ± 0.29 MJ kg-1 DM) (n = 12). Although stocking density did not affect the worms’ nitrogen and phosphorus contents, small worms had a higher mean proportion of nitrogen and phosphorus (10.57 ± 0.17 % and 0.70 ± 0.01 % of DM, respectively) than large worms (9.99 ± 0.12 % and 0.65 ± 0.01 % of DM, respectively) (n = 6). More lipid was present in large worms grown at the medium density (11.20 ± 0.19 %) compared with the high density (9.50 ± 0.31 %) and less was generally found in small worms (7.1-7.6 % of DM). Mean cholesterol and total phospholipid levels were 5.24 ± 0.15 mg g-1 and 13.66 ± 2.15 mg g-1 DM, respectively (n = 12). Of the specific phospholipids tested, phosphatidyl-serine or sphingomyelin were below detection limits (<0.05 mg g-1), whilst mean levels of phosphatidyl-ethanolamine, phosphatidyl-inositol, phosphatidyl-choline and lysophosphatidyl-choline were 6.89 ± 1.09, 0.89 ± 0.26, 4.04 ± 1.17 and 1.84 ± 0.37 mg g-1, respectively (n = 12). Culture density generally had a more pronounced effect on phospholipid contents than did size of worms. By contrast, worm size had a more pronounced effect on total fatty acid contents, with large worms containing significantly higher (P<0.001) levels on a DM basis (46.88 ± 2.46 mg g-1) than smaller worms (27.76 ± 1.28 mg g-1). A very broad range of fatty acids were detected with palmitic acid being the most heavily represented class (up to 14.23 ± 0.49 mg g-1 DM or 27.28 ± 0.22 % of total fatty acids). Other heavily represented classes included stearic acid (7.4-8.8 %), vaccenic acid (6.8-7.8 %), arachidonic acid (3.5-4.4 %), eicosapentaenoic acid (9.9-13.8 %) and docosenoic acid (5.7-7.0 %). Stocking density did not affect (P>0.05) the levels of amino acids present in polychaete DM, but there was generally less of each amino acid tested on a weight per weight basis in large worms than in small worms. This difference was significant (P<0.05) for the most heavily represented classes being glutamic acid (73-77 mg g-1), aspartic acid (50-54 mg g-1), and glycine (46-53 mg g-1). These results demonstrate how this polychaete species can be planted and sorted at harvest according to various strategies aimed at providing biomass with specific physical and nutritional qualities for different uses.

Solubilities of Hexadecanoic and Octadecanoic Acids in Supercritical CO2 With and Without Cosolvents

The solubilities of hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid) in supercritical carbon dioxide without cosolvents and with two cosolvents, namely, ethanol and 3-methyl-1-butanol, were determined at (308 and 318) K at pressures varying from (12.8 to 22.6) MPa. The solubility data, in both the absence and presence of cosolvents, were correlated by a model proposed by Mendez-Santiago and Teja.

Mixed saturated-unsaturated alkyl-chain assemblies: Solid solutions of zinc stearate and zinc oleate

The linear saturated stearic acid and the bent mono-unsaturated oleic acid do not mix and form solid solutions. However, the zinc salts of these acids can. From X-ray diffraction and DSC measurements we show that the layered zinc stearate and zinc oleate salts form a homogeneous solid solution at all composition ratios. The solid solutions exhibit a single melting endotherm, with the melting temperature varying linearly with composition but with the enthalpy change showing a minimum. By monitoring features in the infrared spectra that are characteristic of the global conformation of the hydrocarbon chain, and hence can distinguish between stearate and oleate chains, it is shown that solid solution formation is realized by the introduction of gauche defects in a fraction of the stearate chains that are then no longer linear. This fraction increases with oleate concentration. It has also been possible from the spectroscopic measurements to establish a quantitative relation between molecular conformational order and the thermodynamic enthalpy of melting of the solid solutions.

Lipid composition of the silkworm Bombyx mori L

The constituents of silkworm fat were studied in detail. An unsaturated fat with a high concentration of phospholipid was generally observed. Its iodine value increased during metamorphosis. The free fatty acid concentration likewise increased from the spinning larvae to the moth stage. Analyses of silkworm organs revealed that the fat body had the most fat and the least free fatty acids, whereas haemolymph contained the least fat. Silk glands contained the maximum phospholipid percentage. Stearic acid predominated in those tissues that had a high percentage of phospholipid. Stearic acid was the predominant saturated fatty acid in both the phospholipids and lecithin, and it accounted for 35–50 per cent of the free fatty acids of all the tissues. Q10 was the ubiquinone present; also found were ubichromenol and tocopherol. Results show that silkworm sterol may be cholesterol. Intestines contained the maximum quantities of sterol, ubiquinone, ubichromenol, and tocopherol. The composition of silkworm phospholipids varies considerably from those of other insects, but lecithin is comparable in its composition with lecithins of other animals. The phospholipids had with them a highly complexed protein along with a polysaccharide. In experiments with snake venoms unsaturated fatty acids were found to be predominantly released from silkworm lecithin.

Kinetics of copolyurethane network formation

Cure kinetics for the formation of copolyurethane networks of various compositions based on hydroxy-terminated polybutadiene(HTPB), poly(12-hydroxy stearic acid-co-TMP) ester polyol(PEP), and different isocyanates has been studied through viscosity build up during the cure reaction. The viscosity (N)-time (t) plots conform to the equation N = ae(bt), where a and b are empirical constants, dependent on the composition and the nature of the polyols and the isocyanates. The rate constants (b) for viscosity build up, evaluated from the slopes of dN/dt versus N plots at different temperatures, were found to vary significantly from 0.0073 to 0.25 min(-1); and the activation energies for gelation were found to be in the range 20 to 40 kJ mol(-1). The results have been interpreted in terms of the dependence of the rate constants on structural characteristics of the prepolymers. (C) 1997 John Wiley & Sons, Inc.

Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

Bioremediation and lipid synthesis through mixotrophic algal consortia in municipal wastewater

Algae grown in outdoor reactors (volume: 10 L and depth: 20 cm) were fed directly with filtered and sterilised municipal wastewater. The nutrient removal efficiencies were 86%, 90%, 89%, 70% and 76% for TOC, TN, NH4-N, TP and OP, respectively, and lipid content varied from 18% to 28.5% of dry algal biomass. Biomass productivity of similar to 122 mg/l/d (surface productivity 24.4 g/m(2)/d) and lipid productivity of similar to 32 mg/l/d were recorded. Gas chromatography and mass spectrometry (GC-MS) analyses of the fatty acid methyl esters (FAME) showed a higher content of desirable fatty acids (bearing biofuel properties) with major contributions from saturates such as palmitic acid C16:0; similar to 40%] and stearic acid C18:0; similar to 34%], followed by unsaturates such as oleic acid C18:1(9); similar to 10%] and linoleic acid C18:2(9,12); similar to 5%]. The decomposition of algal biomass and reactor residues with an exothermic heat content of 123.4 J/g provides the scope for further energy derivation. (C) 2014 Elsevier Ltd. All rights reserved.

Water Vapor Barrier Material by Covalent Self-Assembly for Organic Device Encapsulation

Development of barrier materials for organic device encapsulation is of key interest for the commercialization of organic electronics. In this work, we have fabricated barrier films with ultralow water vapor permeabilities by reactive layer-by-layer approach. Using this technique, alternative layers of polyethylene imine and stearic acid were covalently bonded on a Surlyn film. The roughness, transparency and thickness of the films were determined by atomic force microscopy, UV-visible spectroscopy and scanning electron microscopy, respectively. Water vapor transmission rates through these films and the ability of these films to protect the organic photovoltaic devices was investigated. The films with covalently assembled bilayers exhibited lower water vapor transmission rates and maintained higher organic photovoltaic device efficiencies compared to the neat Surlyn film.

Reactive interlayer based ultra-low moisture permeable membranes for organic photovoltaic encapsulation

Reactive interlayers consisting of zero valent iron and copper nanoparticles have been successfully incorporated into Surlyn films to fabricate moisture barrier materials with reduced water vapor permeabilities. The reactive nanoparticles dispersed in stearic acid were employed as the interlayers due to their ability to react with moisture. The water vapor transmission rates through the fabricated barrier films with reactive iron and copper interlayers decreased by over 4 orders of magnitude when compared to neat Surlyn. The flexibility and transparency of the barrier films have been evaluated by tensile and UV-visible experiments. Moreover, the accelerated aging studies conducted in accordance with the ISOS-III protocol confirmed the increased lifetimes of the organic photovoltaic (OPV) devices encapsulated with these reactive barrier films.

Nano-Tribological Study on a Super-Hydrophobic Film Formed on Rough Aluminum

A novel super-hydrophobic stearic acid (STA) film with a water contact angle of 166° was prepared by chemical adsorption on aluminum wafer coated with polyethyleneimine (PEI) film. The micro-tribological behavior of the super-hydrophobic STA monolayer was compared with that of the polished and PEI-coated Al surfaces. The effect of relative humidity on the adhesion and friction was investigated as well. It was found that the STA monolayer showed decreased friction, while the adhesive force was greatly decreased by increasing the surface roughness of the Al wafer to reduce the contact area between the atomic force microscope (AFM) tip and the sample surface to be tested. Thus the friction and adhesion of the Al wafer was effectively decreased by generating the STA monolayer, which indicated that it could be feasible and rational to prepare a surface with good adhesion resistance and lubricity by properly controlling the surface morphology and the chemical composition. Both the adhesion and friction decreased as the relative humidity was lowered from 65% to 10%, though the decrease extent became insignificant for the STA monolayer.

Micro- and macro-tribological study on a self-assembled dual-layer film

A novel self-assembled dual-layer film as apotential excellent lubricant for micromachines was successfully prepared on single-crystal silicon substrate by chemical adsorption of stearic acid (STA) molecules on self-assembled monolayer of 3-aminopropyltri

Efeito dos óleos vegetais de linhaça e de amendoim sobre a vulcanização da borracha natural (NR)

O efeito de dois óleos vegetais, óleo de linhaça e óleo de amendoim, em composições de borracha natural (NR) foi avaliado. Um sistema de vulcanização convencional foi escolhido e, após a mistura, os parâmetros reométricos (Sℓ, Sh, ts1 e t90) foram analisados. A cinética de vulcanização foi estudada através de dois modelos cinéticos um modelo simplificado e o modelo proposto por Coran. Os resultados experimentais permitem concluir que os óleos vegetais sozinhos ou combinados são capazes de atuar como ativadores e, juntamente com os demais ingredientes da composição, de vulcanizar a borracha. No entanto, uma densidade de ligações cruzadas satisfatória só é atingida quando o ácido esteárico está presente. O modelo cinético de Coran permitiu também estudar os diferentes estágios da vulcanização e verificar que a etapa crítica do processo é a formação do precursor de ligações cruzadas (A → B). Provavelmente, a presença significativa de ácidos graxos insaturados na composição dos óleos vegetais (principalmente, os ácidos oléico e linolênico) permita reações laterais não esperadas, o que diminui o rendimento final em ligações cruzadas dos vulcanizados.