Mat formation and unstable flows of highly filled suspensions in capillaries and continuous processors

Suspensions, which are filled at loading levels approaching their maximum packing fractions, present special processing challenges. The flow and deformation behavior of such highly filled suspensions are dominated by strong slip effects. Furthermore, during pressure driven flows of these suspensions, the polymer matrix can filter out, giving rise to demixing and unstable flows. In this study, the capillary flow and extrusion of highly filled suspensions of ammonium sulfate and other salt fillers in a poly(butadiene acrylonitrile acrylic acid), PBAN matrix were investigated. The experimentally observed instabilities were elucidated in conjunction with a proposed mechanism, involving slip and filtration rates. This mechanism suggested greater affinity to unstable flows with relatively lower matrix shear viscosity, greater particle size of the filler, and greater convergence ratio; all of which were experimentally verified.     

Impact modified epoxy/montmorillonite nanocomposites: synthesis and characterization

Diglycidyl ether of bisphenol A type epoxy resin-polyether polyol-organically treated montmorillonite ternary nanocomposites were synthesized in this study. The effects of addition of polyether polyol as an impact modifier on morphological, thermal and mechanical properties of nanocomposites were investigated by X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry, impact and tensile testing. The results showed that organically treated montmorillonite is intercalated by epoxy, since the interlayer spacing expanded from 1.83 to 3.82 nm upon nanocomposite synthesis. The addition of polyether polyol impact modifier had no effect on the interlayer spacing. SEM examination showed that polyol forms an immiscible phase in the epoxy matrix. Thermal characterization of nanocomposites indicated an increase in T_g with respect to both polyether polyol and montmorillonite contents. The impact strength of the samples with no clay was improved approximately 160% upon adding 7 wt% polyether polyol. In polyether polyol modified nanocomposites, the impact and tensile strengths decreased with respect to increasing amount of montmorillonite and showed a maximum with respect to the polyether polyol content at constant clay loading. The Young's modulus of the nanocomposites exhibited an increase with respect to the montmorillonite loading and showed a maximum with respect to the polyol content at each clay loading.     

Viscoelastic properties of reactive and non‐reactive blends of ethylene‐methyl acrylate copolymers with styrene‐maleic anhydride copolymer

The effects of compatibilizing reactions on the viscoelastic properties and morphology of ethylene‐methyl acrylate copolymers were studied. Potentially reactive blends of styrene‐maleic anhydride copolymer (SMAH) and a terpolymer of ethylene/methyl acrylate/glycidyl methacrylate (E‐MA‐GMA) were compared with a non‐reactive blend of SMAH and an ethylene/methyl acrylate (E‐MA) copolymer with similar rheological properties. Melt mixing was carried out in a batch mixer and in a co‐rotating twin screw extruder. The morphology of the reactive blends showed smaller domain sizes than the non‐reactive blends, and the viscoelastic properties of the blends were very different. The storage and loss moduli and the complex viscosity of the reactive blends were greater than those of non‐reactive blends. The reactive blends had a higher zero shear viscosity, plateau modulus and mean relaxation time than their non‐reactive counterparts, indicating a higher degree of melt elasticity. The melt elasticity was maximum at 25% functionalized ethylene‐methyl acrylate concentration.     

Polystyrene–organoclay nanocomposites prepared by melt intercalation,in situ,and masterbatch methods

In this study, polystyrene (PS)/montmorillonite nanocomposites were prepared by melt intercalation, in situ polymerization, and masterbatch methods. In the masterbatch method, as the first step, a high clay content composite of PS–organoclay (masterbatch) was prepared by in situ polymerization, and then the prepared masterbatch was diluted to desired compositions with commercial PS in a twin‐screw extruder. The structure and mechanical properties of the nanocomposites were examined. X‐ray diffraction (XRD) analysis showed that the d‐spacing of the in situ formed nanocomposites increased from 32.9 Å for the organoclay powder to 36.3 and 36.8 Å respectively in nanocomposites containing 0.73 and 1.6 wt% organoclay, indicating intercalation. However, the d‐spacing of the other prepared materials remained nearly unchanged when compared with pure organoclay powder. Thus, at these low clay contents, in situ formed nanocomposites showed the best improvement in mechanical properties including tensile, impact strength, and Young's modulus. In situ polymerization method did not prove to be efficient at high clay loadings in terms of intercalation and mechanical properties. At high clay loadings, the effects of the three methods in promoting mechanical properties were not significantly different from each other. POLYM. COMPOS., 27:249–255, 2006. © 2006 Society of Plastics Engineers     

Single stage hydrogen production from cellulose through photo-fermentation by a co-culture of Cellulomonas fimi and Rhodopseudomonas palustris

Biohydrogen production from cellulose by a bacterial co-culture is a potentially promising approach for producing bioenergy from a low cost substrate. The use of a cellulolytic bacterium, Cellulomonas fimi, permits cellulose conversion and the in situ production of substrate for growth and hydrogen production by the photosynthetic bacterium Rhodopseudomonas palustris. Response surface methodology (RSM) with a Box-Behnken design (BBD) was used to examine variations in the key parameters: substrate (cellulose) concentration, yeast extract concentration and the microorganism ratio (Rps. palustris/C. fimi). For the co-culture of R. palustris and C. fimi the highest hydrogen production (44 mmol H₂/L) was achieved at the highest substrate concentration (5 g/L); however, the highest hydrogen yield (3.84 mol H₂/mol glucose equivalent) was observed at the lowest cellulose concentration and highest microorganism ratio. High COD removal efficiencies, over 70%, were achieved over a wide range of conditions and were positively affected by the concentration of yeast extract.     

Spectrofluorometric analysis and electrical conductivities of styrene and methyl methacrylate polymers

Conductive polymers were obtained by using a new polymerization method where UV‐light was used as a photochemical initiator. To obtain high molecular weights, optimum irradiation times were determined. The luminescence properties of polymers have been found to be useful for their identification. The use of luminescence spectroscopy as an analytical technique for polymer identification involves the measurement of fluorescence emission spectrum, which is obtained by exciting the polymer with UV‐radiation. Fluorescence emission spectra of polystyrene (PS) and polymethyl methacrylate (PMMA) samples were taken at room temperature at excitation wavelengths at 290 nm and 292 nm, respectively. PPMA was prepared with different molecular weights, and the intensity of the fluorescence emission was correlated with polymer chain length. Conductivity versus molecular weight relation was established for each polymer. The plots obtained between conductivities and molecular weights can be used as a calibration curve. From the plot of emission intensity against polymer molecular weights, the molecular weights of unknown polymeric samples can be determined. The most efficient irradiation times were determined by using conductivity versus irradiation time plots. Conductivity versus temperature change of the polymeric samples at different temperatures was determined. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamic risk analysis using alarm databases to improve process safety and product quality: Part II—Bayesian analysis

Part II presents step (iii) of the dynamic risk analysis methodology; that is, a novel Bayesian analysis method that utilizes near‐misses from distributed control system (DCS) and emergency shutdown (ESD) system databases—to calculate the failure probabilities of safety, quality, and operability systems (SQOSs) and probabilities of occurrence of incidents. It accounts for the interdependences among the SQOSs using copulas, which occur because of the nonlinear relationships between the variables and behavior‐based factors involving human operators. Two types of copula functions, multivariate normal and Cuadras–Augé copula, are used. To perform Bayesian simulation, the random‐walk, multiple‐block, Metropolis–Hastings algorithm is used. The benefits of copulas in sharing information when data are limited, especially in the cases of rare events such as failures of override controllers, and automatic and manual ESD systems, are presented. In addition, product‐quality data complement safety data to enrich near‐miss information and to yield more reliable results. Step (iii) is applied to a fluidized‐catalytic‐cracking unit (FCCU) to show its performance. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Ethylene‐methyl acrylate‐glycidyl methacrylate toughened poly(lactic acid) nanocomposites

Poly (lactic acid) (PLA) was melt blended in a twin screw extruder using an ethylene‐methyl acrylate‐glycidyl methacrylate rubber as a toughener. PLA/rubber blends were immiscible as observed by scanning electron microscopy. Impact strength and ductility of PLA were improved by the addition of the rubber at the expense of strength and stiffness. An organo‐montmorillonite (OMMT) was used at 2 wt % to counteract the negative effect of the rubber on modulus, and balanced properties were observed at 10 wt % rubber content. X‐ray diffraction and transmission electron microscopy revealed the formation of intercalated/exfoliated structure in the ternary nanocomposites. Thermal behavior analysis indicated that the degree of crystallinity is slightly affected by the clay and the rubber. Both the clay and the rubber decreased the crystallization temperature of PLA and acted as nucleating agents for PLA. The viscosity of the mixtures as measured by melt flow index was highly influenced by the rubber and the OMMT. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Determination of Rosmarinic Acid by High-Performance Liquid Chromatography and Its Application to Certain Salvia Species and Rosemary

This study describes a method development for the determination of rosmarinic acid (RA) by using a gradient high-performance liquid chromatography (HPLC) and its application to certain plant materials. The analysis was performed by utilizing a two solvents system [A: methanol/water/formic acid (10:88:2; v:v:v); B: methanol/water/formic acid (90:8:2; v:v:v)] on a reverse-phase column. The flow rate and injection volume were 1 ml min⁻¹ and 10 μl, respectively. Signals were detected at 280 nm. In addition, an internal standard (IS) technique was applied for the analysis of RA to increase precision, and propylparaben was employed for this purpose. The repeatability results as RSD% were 1.66, 1.17 and 1.26 for intra-day and 1.38 was for inter-day with the employment of (3.67 × 10⁻⁵ M) RA. A limit of linearity (LOL) was observed in a wide (1.13 × 10⁻⁵–5.65 × 10⁻⁴ M) concentration range. Linearity parameters were also examined in the range of 5.95 × 10⁻⁶–7.14 × 10⁻⁵ M RA, and very good correlation was observed. The limit of detection (LOD) and limit of quantification (LOQ) (for inter-day) were 1.60 × 10⁻⁶ M (signal/noise [S/N] = 3.3) and 4.80 × 10⁻⁶ M (S/N = 10), respectively. The method was applied to the extracts of certain Lamiaceae plants (Salvia candidissima Vahl. subsp. candidissima, S. sclarea L., S. verticillata L. subsp. verticillata and R. officinalis L.), and reasonable results were obtained.