Monitoring abiotic degradation of branched polyethylenes formulated with pro-oxidants through different mechanical tests

The mechanical properties of two linear low density and low density polyethylenes containing a pro-oxidant additive were monitored during accelerated aging (60 °C in a convection oven) and weather exposure. Tearing tests (trouser) were performed for the first time in polyethylenes subjected to oxo-degradation revealing a transition from an extensible to a non-extensible material, at exposure times when standard tensile tests were not able to detect any changes in the materials. The essential work of fracture (EWF) technique was also applied and the results were in agreement with those of trouser tests. The specific essential work of fracture first increased with exposure time until the sample experienced a transition to a less ductile state where EWF was no longer applicable. EWF and trouser tear tests were more sensitive detecting the onset of degradation probably because they employ notched specimens that impose more critical stress concentration conditions than conventional tensile tests.     

Emulsions of Heavy Crude Oils. II. Viscous Responses and Their Influence on Emulsion Stability Measurements

The stability of 30 heavy crude oil emulsions was studied in a parallel-plate laboratory coalescer (DC field). Particularly, viscous responses and their influence on the emulsion stability measurements were investigated. In addition to highlighting previous results from the same experimental setup and discussing these based on recent experience, new results at different temperatures and volume fractions of water were presented. A new semi-empirical model for the characteristic time of the destabilization process was presented. The electrical forces were modelled with a point-dipole approximation and the hydrodynamic resistance to droplet transport was modelled with an empirical term including the logarithmic viscosity of the oil phase. The new model clearly performed much better than the previous model, particularly for very viscous crude oils. Studies of the performance of industrial electrocoalescers have showed that simple electrostatic theory can potentially explain complex separation phenomena when the resistance to the coalescence step is reduced by an efficient demulsifier. The ultimate goal is to build a model for both the laboratory setup and the industrial coalescer so that laboratory experiments can be used to predict the behavior of the industrial process.     

Biofuels–Renewable Energy Sources: A Review

Biodiesel is biodegradable and nontoxic, and it significantly reduces toxic and other emissions when burned as a fuel. The advantages of biodiesel as diesel fuel are its portability, ready availability, renewability, higher combustion efficiency, non-toxicity, higher flash point, and lower sulfur and aromatic content, higher cetane number, and higher biodegradability. The major disadvantages of biodiesel are its higher viscosity, lower energy content, higher cloud point and pour point, higher nitrogen oxide (NO_x) emissions, lower engine speed and power, injector coking, engine compatibility, high price, and greater engine wear. The technical disadvantages of biodiesel/fossil diesel blends include problems with fuel freezing in cold weather, reduced energy density, and degradation of fuel under storage for prolonged periods. The sources of biodiesel are vegetable oils and fats. The direct use of vegetable oils and/or oil blends is generally considered to be unsatisfactory and impractical for both direct injection and indirect type diesel engines because of their high viscosities and low volatilities injector coking and trumpet formation on the injectors, higher level of carbon deposits, oil ring sticking, and thickening and gelling of the engine lubricant oil, acid composition. Biodiesel is obtained by transesterifying triglycerides with methanol. A popular variation of the batch transesterification process which needs high alcohol/acid ratio (several separation problems and high corrosivity and toxicity) is the use of continuous stirred tank reactors in series. This continuous process is heterogeneous and is based on reactive distillation. The key factor is the selection of the right and effective solid catalyst which leads to reduction of energy consumption and investments at all.     

Rheological Properties of Particle-Stabilized Emulsions

We have studied the rheological properties of fumed silica particle-stabilized emulsions. Two particles of different polarity were considered, the first more hydrophilic “Aerosil R7200,” the second more hydrophobic “Aerosil R972.” These particles flocculate and probably form a network at the investigated concentration. The flow curves of emulsions stabilized by a single type of particles exhibit yield stress, shear-thinning behavior and thixotropy. Moreover they display rheological features typical of gels. These features are attributed to strengthening of the particle network by droplets. Moreover the rheological properties of w/o emulsions stabilized by hydrophobic are similar to the ones of o/w emulsions stabilized by hydrophilic particles. The rheological properties of o/w emulsions stabilized by mixtures of hydrophilic and hydrophobic particles have then been studied by keeping the total particle concentration constant and varying the mass ratio between particles. The results show that when the hydrophobic particle concentration increases, the viscosity and stability of emulsions decrease establishing evidence that the network is weakened due to preferential orientation of hydrophobic particles towards the oil phase.     

INDUSTRIAL NEWS

Interactions between monolayers of trilaurylamine (TLA) and various water-soluble corrosion, hydrate and scale inhibitors, as well as acetic acid and FeCl₂, have been studied by means of the Langmuir technique, The water-soluble compounds were present in the subphase before TLA was spread. Their influence on the monolayer properties were measured by means of surface pressure-area ( k-A) isotherms and constant surface pressure-area relaxation measurements. All the added water soluble species gave rise to monolayer expansion. The monolayer expansion observed for TLA at pH 1, increased when FeCl₂ was added to the subphase at the same pH. Polyethyleneglycols with molecular weight higher than 200 destabilized totally the TLA-monolayer, probably due to bending and folding into multilayers. Monolayer expansion and film instability increased with increased acetic acid concentrations. The destabilization mechanism in this case was most likely due to a combination of nucleation and dissolution of film components into the subphase. The corrosion inhibitor Dyno KI 384 had a higher surface activity than TLA. Hence the monolayer     

Influence of Interfacial Tension on Seeded Calcium Carbonate Scale Precipitation: Effect of Adsorbed Asphaltenes

Clay particles with adsorbed asphaltenes, which are commonly found in produced water, have been used as seed particles during precipitation of calcium carbonate in order to determine whether such particles may influence the kinetics of precipitation. The results show that the presence of the adsorbed asphaltenes accelerates the precipitation, and there is also a significant difference between different types of adsorbed asphaltenes. The adsorption of asphaltenes at the seed surface leads to a significant increase in the interfacial tension between the seed surface and the aqueous solution, and calcium carbonate therefore precipitates at the seed surface in order to reduce this high interfacial tension.     

Rheological Properties of Model and Crude Oil Systems when Wax Precipitate under Quiescent and Flowing Conditions

Wax precipitation and deposition is a recurring challenge in transportation of crude oil, and increased knowledge about the behavior of such systems is necessary. Microscopy and differential scanning calorimetry were used to follow the crystallisation of wax for two model systems. The amount of solid was also determined by the latter method as well. The flow and viscoelastic behavior were investigated around the wax precipitation temperature, and the yield stress was determined both after dynamic and static cooling. Interpretation of the results was carried out in view of crystal growth and microstructure of the wax crystals. The variables that were studied were wax composition, amount of wax and thermal and shear history.     

Stability of Water/Crude Oil Systems Correlated to the Physicochemical Properties of the Oil Phase

A characterization of 30 crude oils has been performed to determine the relative level of influence that individual parameters have over the overall stability of w/o emulsions. The crude oils have been analyzed with respect to bulk and interfacial properties and the characteristics of their w/o emulsions. The parameters include compositional properties, acidity, spectroscopic signatures in the infrared and near‐infrared region, density, viscosity, molecular weight, interfacial tension, dilational relaxation, droplet size distribution, and stability to gravitationally and electrically induced separation. As expected, a strong covariance between several physicochemical properties was found. Near‐infrared spectroscopy proved to be an effective tool for crude oil analysis. In particular, we have showed the importance of the hydrodynamic resistance to electrically‐induced separation (static) in heavy crude oil‐water emulsions. A rough estimate of the drag forces and dielectrophoretic forces seemed to capture the difference between the 30 crude oils. Given enough time, water‐in‐heavy oil emulsions could be destabilized even at very low electric field magnitude (d.c.). When droplets approach each other in an inhomogeneous electric field, strong dielectrophoretic forces disintegrate the films and result in coalescence. The relative contribution from film stability to the overall emulsion stability may therefore be very different in a gravitational field compared to that in an electrical field.     

Oil-Water Partitioning of a Synthetic Tetracarboxylic Acid as a Function of pH

The oil-water partitioning of a synthetic tetraacid acting as a model compound for indigenous C₈₀-C₈₂ ARN acids has been studied as a function of pH, ionic strength and type of monovalent counterion. Experimental data obtained with ultraviolet-visible and HPLC/UV analyses have been fitted to thermodynamic models based on one, two or four dissociation steps to obtain o/w partition coefficients (K _wo ) of the fully protonated acid between chloroform and aqueous solutions, and its apparent acidity constant(s), pK _a. As the study is conducted above the CMC of the tetraacid, in general high apparent acidity constants were obtained in the range from 6 to 8 resulting from micellization equilibria. K _wo values were obtained in the range from 10^?3 to 10^?4, and decreasing with increasing salinity. At 50 mM K⁺, no conclusions could be made regarding the number of distinguishable dissociation steps, while at higher ionic strength (184 mM and 452 mM K⁺) and at 184 mM Na⁺ a model with two dissociation steps provided good fits to the experimental data. The first step was found to be given by a pK _a ≈ 6.6–6.8 and the second dissociation step at pK _a values ≈ 7.8–8.3. The two-step mechanism supports previous results obtained by potentiometric titrations. No significant difference in the o/w behavior was observed when changing the counterion from potassium to sodium. The main partitioning of the tetraacid in the aqueous phase occurred above pH 8, where the fully deprotonated acid was formed.     

Rapid Removal of Organics and Oil Spills from Waters Using Silicone Rubber “Sponges”

We have developed a simple, robust, and efficient technology utilizing cheap and recoverable materials based on commercially available silicone elastomer networks for removing organic solvents and crude oil from waters. Hydrophobic and oleophilic properties of silicone elastomers endow poly(dimethyl siloxane) (PDMS) with the capacity to absorb a large variety of organics, including benzene (B), toluene (T), ethylbenzene (E), and xylene (X), commonly referred to as BTEX, and also crude oils, while at the same time enabling the organic “sponges” to float on waters, which facilitates straightforward handling. We developed a method for generating PDMS particles with variable sizes (ranging from hundreds nanometers to few millimeters) by drop-wise depositing siloxane/cross-linker mixtures into warm water, a process which leads to the cross-linking of the PDMS components. We have tested the capability of the PDMS particles to remove toluene and benzene from water. We also performed similar experiments by utilizing PDMS sheets. In both instances we observed a rapid sorption of the organic phase into PDMS; the amount of absorbed organic solvent depended on the concentration in water and the total mass (volume) of PDMS and did not depend on the geometry of the PDMS “sponge.” In addition, we have examined the uptake of toluene and benzene from toluene/benzene (T/B) mixtures dissolved in water. Our results indicate that the amount of benzene absorbed from the T/B mixtures into PDMS increases relative to the uptake from pure benzene/water solutions. This behavior is associated with toluene acting as a “surfactant” that effectively replaces the more unfavorable PDMS/B contacts with less costly T/B ones. Finally, a simple experiment demonstrates qualitatively that PDMS is also capable of removing crude oils from oil-contaminated waters.