The influence of the chemical nature of dispersed phase on stability in oil-in-water emulsions

Some of the problems arising from the inherent instability of emulsions are discussed. Aspects of emulsion stability are described and particular attention is given to the influence of the chemical nature of the dispersed phase on adsorbed film structure and stability, Emulsion stability has been measured by a photomicrographic technique. Electrophoresis, interfacial tension and droplet rest-time data were also obtained. Emulsions were prepared using a range of oils, including aliphatic and aromatic hydrocarbons, dispersed In a solution of sodium dodecyl sulphate. In some cases a small amount of alkane or alkanol was incorporated into the oil phase. In general the findings agree with the classical view that the stability of oil-in-water emulsions is favoured by a closely packed interfacial film and appreciable electric charge on the droplets. The inclusion of non-ionic alcohol leads to enhanced stability, presumably owing to the formation of a "mixed" interfacial film which is more closely packed and probably more coherent than that of the anionic surfactant alone. In some instances differences in stability cannot he accounted for simply by differences in interfacial adsorption or droplet charge. Alternative explanations are discussed and it is postulated that the coarsening of emulsions may occur not only hy coalescence but also through the migration of oil from small droplets to larger ones by molecular diffusion. The viability of using the coalescence rates of droplets at a plane interface as a guide to emulsion stability has been researched. The construction of a suitable apparatus and the development of a standard testing procedure are described. Coalescence-time distributions may be correlated by equations similar to those presented by other workers, or by an analysis based upon the log-normal function. Stability parameters for a range of oils are discussed in terms of differences in film drainage and the natl1re of the interfacial film. Despite some broad correlations there is generally poor agreement between droplet and emulsion stabilities. It is concluded that hydrodynamic factors largely determine droplet stability in the systems studied. Consequently droplet rest-time measurements do not provide a sensible indication of emulsion stability,

Selective oxidation of crotyl alcohol over Pd(111)

The selective oxidation of crotyl alcohol has been explored over a Pd(111) model catalyst. At low temperatures, the alcohol adsorbs intact with the C=C bond parallel to the surface. Activation likely proceeds through an allyl alkoxide intermediate that follows two distinct reaction channels. Over the clean surface, ∼90% of the alcohol oxidizes to surface bound crotonaldehyde above 200 K, which subsequently all decarbonylates to propene and CO at room temperature. The minor reaction channel involves C-O scission to 2-butene and water. While some of these undesired reactively formed alkene products desorb around 300 K, the majority dehydrogenate to irreversibly bound carbon above 380 K. This latter decomposition pathway is unlikely to be important at the low temperatures utilized in liquid-phase crotyl alcohol oxidation over supported palladium catalysts. Adsorbed CO persists until 430 K and is likely responsible for site-blocking and deactivation of dispersed metallic Pd clusters. Coadsorbed oxygen suppresses crotonaldehyde decarbonylation and promotes its release from the surface. © 2007 American Chemical Society.

(Table T1) N-alkane, n-alcohol and n-fatty acid concentrations in ODP Site 184-1147 and 184-1148 sediments

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 184 in the South China Sea have been identified and quantified. The identified lipids can be ascribed to terrigenous and marine sources. Terrigenous lipids are mainly C27, C29, C31 n-alkanes, C26, C28, C30 n-fatty acids, and n-alcohols, which were derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Marine lipids, mainly C37 and C38 alkenones, C30 diol, and C30 and C32 keto-ols, were from microalgae, notably haptophytes and eustigmatophytes. Elevated concentrations and accumulation rates of both terrigenous and marine lipids in the interval 202-245 meters composite depth (mcd) and 0-166 mcd were postulated to be related to the development of the East Asian monsoon at 6-8 Ma and enhanced variations of the developed East Asian monsoon after 3.2 Ma, respectively. The pronounced late Oligocene input of terrigenous lipids reflects the paleoenvironment of a newly opened, narrow basin, with restricted ocean waters and the proximity of continental runoff.

Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation

Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a significant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A significant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Different butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the different butanol isomers using cyclic voltammetry (CV), indicating a difference in activity and the mechanism of oxidation. The voltammograms of both n-butanol and iso-butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely different features; for example, it did not show any indication of poisoning. Ter-butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OHads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OHads at lower potentials, Pt was modified by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A significant enhancement in the oxidation of the 1° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the bifunctional mechanism on PtSn catalyst. The positive influence of Sn was also confirmed in the PtSn nanoparticle catalyst prepared by the modification of commercial Pt/C nanoparticle and a higher activity was observed for PtSn (3:1) composition. The temperature-dependent data showed that the activation energy for butanol oxidation reaction over PtSn/C is lower than that over Pt/C.

Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Liquid-phase alcohol promoted methanol synthesis from CO2 and H2

Methanol is an important and versatile compound with various uses as a fuel and a feedstock chemical. Methanol is also a potential chemical energy carrier. Due to the fluctuating nature of renewable energy sources such as wind or solar, storage of energy is required to balance the varying supply and demand. Excess electrical energy generated at peak periods can be stored by using the energy in the production of chemical compounds. The conventional industrial production of methanol is based on the gas-phase synthesis from synthesis gas generated from fossil sources, primarily natural gas. Methanol can also be produced by hydrogenation of CO2. The production of methanol from CO2 captured from emission sources or even directly from the atmosphere would allow sustainable production based on a nearly limitless carbon source, while helping to reduce the increasing CO2 concentration in the atmosphere. Hydrogen for synthesis can be produced by electrolysis of water utilizing renewable electricity. A new liquid-phase methanol synthesis process has been proposed. In this process, a conventional methanol synthesis catalyst is mixed in suspension with a liquid alcohol solvent. The alcohol acts as a catalytic solvent by enabling a new reaction route, potentially allowing the synthesis of methanol at lower temperatures and pressures compared to conventional processes. For this thesis, the alcohol promoted liquid phase methanol synthesis process was tested at laboratory scale. Batch and semibatch reaction experiments were performed in an autoclave reactor, using a conventional Cu/ZnO catalyst and ethanol and 2-butanol as the alcoholic solvents. Experiments were performed at the pressure range of 30-60 bar and at temperatures of 160-200 °C. The productivity of methanol was found to increase with increasing pressure and temperature. In the studied process conditions a maximum volumetric productivity of 1.9 g of methanol per liter of solvent per hour was obtained, while the maximum catalyst specific productivity was found to be 40.2 g of methanol per kg of catalyst per hour. The productivity values are low compared to both industrial synthesis and to gas-phase synthesis from CO2. However, the reaction temperatures and pressures employed were lower compared to gas-phase processes. While the productivity is not high enough for large-scale industrial operation, the milder reaction conditions and simple operation could prove useful for small-scale operations. Finally, a preliminary design for an alcohol promoted, liquid-phase methanol synthesis process was created using the data obtained from the experiments. The demonstration scale process was scaled to an electrolyzer unit producing 1 Nm3 of hydrogen per hour. This Master’s thesis is closely connected to LUT REFLEX-platform.

Separation and identification fresh water leeches of waters resources in Kordistan Province

In the primary studying, known leeches have included into free living and parasitic which the parasitic group, besides of direct impacts like: growth detraction, anemia, making wound in the connecting part with the skin, with making plat for secondary bacterial and molding infections in the toll place, is able to cause to transfer blood flagellate and virus to the fish too. Therefore, by accusing information related to fauna leeches of each area a risk factor from the viewpoint of the possibility of being or accusing transferred diseases by these leeches, one can predict and forehand about them. Freshwater leeches of Iran to present accurate recognition (morphological, molecular) have not been, and there are some limited reports from different parts of the country about them. One of the areas that its leeches have not been identified yet is Kurdistan, By having five latrines and big permanent rivers and 32000 springs and a lot of deep and semi-deep wells and this province is a convenient bed for growing aquatics in the country. Therefore, identifying risk factors for development of aquaculture on water resources is one important factor to access achieving development goals. For recognizing leeches of this province, some samples from 10 stands were token. Samples from under stones, sticking to the fish, turtles, plants and solid substances in the water were separated and after recording their physical characteristics, calming with 10% ethylic alcohol with 10% formalin become fixed and after painting with Carmen acetic acid by standard keys for 7 species of Helobdella stagnalis, Placobdella costata, Hemiclepsis marginata, Erpobdella octoculata, Hirudo medicinalis, Dina lineate lineata have been identified and described. Which Helobdella stagnalis has the highest distribution in the province and the minimum one is Hirudo medicinalis. However, that the data obtained in leeches in Kurdistan is a relatively complete collection in this research, recognizing fauna of these areas needs more studying. The Placobdella costata and Hemiclepsis marginata sticking to the fish were separated among identified species which showed that these are parasites for the fish. The sticking area of those leeches to the skin was accompanied with scales cast, damage to mucous membranes beneath the parasite and bleeding Was associated with Histopathology studying effect includes observing break and disconnection in the leech connecting place to the epithelial layer of epidermis in the skin, destroyed nucleus in skin Epithelial cells with observing necrosis in ulcerative place become of the leech and the sub acute inflammated penetration until acute necrosis with opening in Dermis layer is observable. Kidney of this fish have changes such as: proliferation, like proliferative kidney disease with increasing proliferative glomerular cells and increasing in membranous cells in Capillary corpuscle, observing necrotic cells in haematopoietic tissue of kidney along with increasing in infiltration of leukocyte's cells generally mono nucluars such as lymphocytes and less poly morpho nucluars such as neutrophiles that are symptoms of disorders causing anemia become of nourishing and sucking blood by the leech and creating a chronic kidney infection that originally root is in another place like the skin. Also Hemorrhagic anemia causes losing RBC's is because of using the host blood by the leech. (In this situation, one can see immature RBC red cells in Peripheral blood. To identify potential carriers of the leech to the viruses, after finding them in recorded stands and putting them in 75% ethanol for viruses cause IPN, VHS, IHN, they were tested by PCR that the conclusion of these experiments approved IPN virus in Hemiclepsis marginata and Hirudo medicinalis. This kind of leeches can act like a mechanical carrier and causing spreading the agent of this disease. It is worth mentioning that studying the pathogenicity of this virus for aquaculture sources, mentioned before needs more research. During the study of infected fish with leeches that was done after preparing bloody slides and staining them, no case blood parasites was observed. During a research about infecting fish experimentally to known leeches it become clear that 5 days after being in aquarium including leeches, samples of sticking Hirudo medicinalis leech to the golden carp with scales cast were observed. Including leeches to the fish started with molting the scales in the sticking area in the fish and fish become too uneasy and by rubbing themselves to the malls and things inside the aquarium, tried to separate them. Finally, after around 30 hours, leeches penetrate the skin, feeding from blood and tissue liquids and cause mortality the fish and then they become separated from them. If the corpse of these fish stayed in the aquarium, the Helobdella stagnalis and Erpobdella octoculata would start feeding them.

Fluorinated surfactants in solution: Diffusion coefficients of fluorinated alcohols in water

Intra-diffusion coefficients of three fluorinated alcohols, 2,2,3,3,3-pentafluoropropan-1-ol (PFP), 2,2,3,3,4,4,4-heptafluorobutan-1-ol (HFB) and 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol (NFP) in water have been measured by the PFG–NMR spin-echo technique as a function of temperature and composition, focusing on the alcohol dilute region. For comparison, intra-diffusion coefficients of 2,2,2- trifluoroethanol (TFE) and HFB have also been measured in heavy water using the same method and conditions. As far as we know, these are the first experimental measurements of this property for these binary systems. Intra-diffusion coefficients for NFP in water and for TFE and HFB in heavy water have also been obtained by molecular dynamics simulation, complementing those for TFE, PFP and HFB reported in a previous work. The agreement between experimental and simulated results for PFP, HFB and NFP in water is reasonable, although presenting higher deviations than for the TFE/water system. From the dependence of the intra-diffusion coefficients on temperature, diffusion activation energies were estimated for all the solutes in water and heavy water.

Swelling properties of alkali-metal doped polymeric anion-exchange membranes in alcohol media for application in fuel cells

Swelling properties of four commercial anion-exchange membranes with different structure have been analyzed in several hydro-organic media. With this target, the liquid uptake and the surface expansion of the membranes in contact with different pure liquids, water and alcohols (methanol, ethanol and 1-propanol), and with water alcohol mixtures with different concentrations have been experimentally determined in presence and in absence of an alkaline medium (LiOH, NaOH and KOH of different concentrations). The alkali-metal doping effect on the membrane water uptake has also been investigated, analyzing the influence of the hydroxide concentration and the presence of an alcohol in the doping solution. The results show that the membrane structure plays an essential role in the influence that alcohol nature and alkaline media has on the selective properties of the membrane. The heterogeneous membranes, with lower density, show higher liquid uptakes and dimensional changes than the homogeneous membranes, regardless of the doping conditions. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Evaporation, seepage and water quality management in storage dams: a review of research methods

One of the most significant sources of water wastage in Australia is loss from small storage dams, either by seepage or evaporation. Over much of Australia, evaporative demand routinely exceeds precipitation. This paper outlines first, methodologies and measurement techniques to quantify the rate of evaporative loss from fresh water storages. These encompass high-accuracy water balance monitoring; determination of the validity of alternative estimation equations, in particular the FAO56 Penman- Monteith ETo methodology; and the commencement of CFD modeling to determine a 'dam factor' in relation to practical atmospheric measurement techniques. Second, because the application of chemical monolayers is the only feasible alternative to the high cost of physically covering the storages to retard evaporation, the use of cetyl alcohol-based monolayers is reviewed, and preliminary research on their degradation by photolytic action, by wind break-up and by microbial degradation reported. Similarly, preliminary research on monolayer visualisation techniques for field application is reported; and potential enhancement of monolayers by other chemicals and attendant water quality issues are considered.

Silk fibroin as a water-soluble bio-resist and its thermal properties

Thermal diffusivity of silk fibroin films, α = (1.6 ± 0.24) × 10-7 m2 s-1, was measured by a direct contact method. It was shown to be reduced down to ∼1 × 10-7 m2 s-1 in the crystallized phase, consistent with the multi-domain composition of β-sheet assemblies. Crystalline silk with β-sheets was made by dipping into alcohol and was used as a positive electron beam lithography (EBL) resist. It is shown by direct IR imaging of the 1619 cm-1 amide-I CO spectral signature and 3290 cm-1 amide-A N-H stretching band that an e-beam is responsible for unzipping β-sheets, which subsequently results in exposed areas returning to a water soluble state. This makes it possible to develop a water-based biocompatible silk resist and use it in lithography applications. The general principles of protein crystallization, traceable to spectral changes in IR amide bands of silk, can be used as a guide for the creation of new protein EBL resists and to quantify the electron dose required for solubility. Foam formation and laser treatments of silk can provide new approaches in surface functionalization and fabrication of 3D bio-scaffolds.

The effects of gender, clothing style, and alcohol consumption on the perception of sexual intent

Background: Alcohol consumption in women is known to be perceived by men as signaling sexual intent. The current study investigated the influence of gender, female clothing style, and female alcohol use on the perception of sexual intent.Method: Eighty-seven men and 72 women viewed a one-minute video of a male–female interaction where clothing style and alcohol use were experimentally manipulated. Participants were then asked to rate the female target on sexual intent.Results: The female actor was rated higher on sexual intent when she was dressed revealingly, and consuming alcohol, compared to when she was wearing conservative clothing and drinking water. Gender differences were not found with respect to the effect of personality characteristics (sociosexual effectiveness, sexually preoccupation, masculine sex role orientation, limited sexual experience and negative sexual attitudes, and low self-esteem and traditional attitudes toward women) on sexual intent.Conclusions: These findings suggest that alcohol may be a social cue used by men to process sexual intent. The implications of the findings are discussed with reference to how women are viewed when consuming alcohol.

Effects of plasticizing and crosslinking on the mechanical and barrier properties of coatings based on blends of starch and poly(vinyl alcohol)

In the last decades, intensive research has been carried out in order to replace oil-based polymers with bio-based polymers due to growing environmental concerns. So far, most of the barrier materials used in food packaging are petroleum-based materials. The purpose of the barrier is to protect the packaged food from oxygen, water vapour, water and fat. The mechanical and barrier properties of coatings based on starch-plasticizer and starch-poly(vinyl alcohol) (PVOH)-plasticizer blends have been studied in the work described in this thesis. The plasticizers used were glycerol, polyethylene glycol and citric acid. In a second step, polyethylene coatings were extruded onto paperboard pre-coated with a starch-PVOH-plasticizer blend. The addition of PVOH to the starch increased the flexibility of the film. Curing of the film led to a decrease in flexibility and an increase in tensile strength. The flexibility of the starch-PVOH films was increased more when glycerol or polyethylene glycol was added than citric acid. The storage modulus of the starch-PVOH films containing citric acid increased substantially at high temperature. It was seen that the addition of polyethylene glycol or citric acid to the starch-PVOH blend resulted in an enrichment of PVOH at the surface of the films. Tensile tests on the films indicated that citric acid acted as a compatibilizer and increased the compatibility of the starch and PVOH in the blend. The addition of citric acid to the coating recipe substantially decreased the water vapour transmission rate through the starch-PVOH coated paperboard, which indicated that citric acid acts as a cross-linker for starch and/or PVOH. The starch-PVOH coatings containing citric acid showed oxygen-barrier properties similar to those of pure PVOH or of a starch-PVOH blend without plasticizer when four coating layers were applied on a paperboard. The oxygen-barrier properties of coatings based on a starch-PVOH blend containing citric acid indicated a cross-linking and increase in compatibility of the starch-PVOH blends. Polyethylene extrusion coating on a pre-coated paperboard resulted in a clear reduction in the oxygen transmission rate for all the pre-coating formulations containing plasticizers. The addition of a plasticizer to the pre-coating reduced the adhesion of polyethylene to pre-coated board. Polyethylene extrusion coating gave a board with a lower oxygen transmission rate when the paperboard was pre-coated with a polyethylene-glycol-containing formulation than with a citric-acid-containing formulation. The addition of polyethylene glycol to pre-coatings indicated an increase in wetting of the pre-coated paperboard by the polyethylene melt, and this may have sealed the small defects in the pre-coating leading to low oxygen transmission rate. The increase in brittleness of starch-PVOH films containing citric acid at a high temperature seemed to have a dominating effect on the barrier properties developed by the extrusion coating process.