Effect of refining on the phenolic composition of crude olive oils

By definition, virgin olive oil is consumed unrefined, although a great proportion of the olive oil produced has to be refined to render it edible. Phenolic compounds are among the substances eliminated during the refining process; in the present work these were characterized by HPLC, and their evolution during the different refining steps was studied. The complete refining process removed most polyphenols from oils, but the behavior of individual compounds at each step also was observed. o-Diphenols (hydroxytyrosol, catechol, and hydroxytyrosol acetate) and flavonoids (luteolin and apigenin) were eliminated first during the alkaline treatment. Tyrosol and 4-ethylphenol remained in the oil until the deodorization step. A large amount of phenolic compounds was discovered in the refining by-products such as soapstocks and deodorization distillates. In the latter streams, the concentrations of tyrosol and 4-ethylphenol reached up to 149 and 3720 mg/kg by-product, respectively. This high level of 4-ethylphenol and its well-known strong off-odor can interfere during further processing of the deodorization distillates, and this must be taken into account when deciding what is to become of them. Similarly, the results of this work open the possibility of recovering phenolic compounds from the “second centrifugation olive oils” by adding a new washing step prior to the refining process. By including this new step, the most polar polyphenols, hydroxytyrosol and tyrosol, will diffuse from oil to water and a concentration of up to 1400 mg/L of hydroxytyrosol may be achieved.     

Does morphology stick? Tailored particle morphologies by swelling polymerization process

Structured dispersion particles suitable for pressure sensitive adhesives (PSA) were synthesized via swelling polymerization technique (EP 359562). Particles consisting of poly(n‐butyl acrylate) copolymerized with different types of carboxylic acids were used as seeds. The final particles were synthesized by swelling polymerization process, using 6 wt % styrene or 6 wt % methyl methacylate. The resulting particle morphology was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). From previous works (Coll Surf A 2001, 183–185, 725–737; J Appl Polym Sci 2004, 91, 2610–2623) where two‐step emulsion polymerization was used on similar particles, it is expected that the particle morphology is affected by the polarity of the monomer used for swelling polymerization because of the phase compatibility (thermodynamic parameter). In this work, the seed particles used were always of a glass transition temperature (T_g) below polymerization temperature. The diffusion of the growing polymer chains from the swelling polymerization is therefore mainly affected by their own T_g and the influence of the carboxy groups on the chain length of the entering radicals (kinetic parameter). The different morphologies of the single particles are discussed qualitatively. The effects of reaction parameters are compared with the results given in the previous work. The structure of the corresponding dispersion films was characterized using AFM. Correlations to macroscopic properties such as the cohesive strength and peel adhesion to different substrates are discussed. The results are also compared with the application properties of the corresponding unmodified particles, statistical copolymers, and to blends with small sized PMMA or PS particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1444–1455, 2006     

Somein situ STM contributions to the characterization of electrochemical systems

We present a critical review on the use of STM as anin situ technique to characterize electrochemical systems based on the work performed in our laboratory. Contributions ofin situ STM studies include: (i) atomic resolution of electrodeposited lead on graphite; (ii) imaging of modifications on metallic electrode surfaces induced by electrochemical oxidation-reduction processes; (iii) imaging of corrosion process on aluminium and Al-Ta alloy electrodes in NaCl solution; (iv) characterization of semiconductor-solution interfaces. These studies allowed: (a) establishment of STM as a technique which, for some systems, yields atomic resolution of metallic surfaces in air and in solution; (b) establishment of a mechanism for the electrochemical growth of oxide films on metal electrodes; (c) establishment of a corresponding mechanism for the reduction of those electrochemically grown oxide films; (d) direct monitoring of corrosion processes on a scale of nm to m; and (e) determination of the presence of surface states and their energy position at the semiconductor-solution interfaces.This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday and in recognition of his outstanding contribution to electrochemistry.     

Morphology of EVA based nanocomposites under shear and extensional flow

Shear and extensional rheological measurements were conducted in conjunction with laser light scattering (LLS) on ethylene‐vinyl acetate copolymer (EVA) nanocomposites. The materials were prepared by melt‐mixing EVA and commercially acquired layered silicates. Wide Angle X‐Ray Scattering (WAXS) was used to ascertain the degree of layer swelling. This could be attributed to the intercalation of polymer chains into the interlayer of the silicates. The nanocomposites prepared were determined to be predominantly intercalated in nature. In shear rheological tests, the nanocomposites exhibited an increase in viscoelastic properties compared to the pure EVA. The extent of this property enhancement was not as pronounced as had been reported in many instances with respect to other polymer nanocomposites. This could be attributed to the absence of a network structure normally observed in an exfoliated system. The extensional rheological tests showed an increase in extensional flow properties. This was confirmed by the LLS, which indicated that the filled systems had higher deformability than the unfilled one. Polym. Eng. Sci. 44:1220–1230, 2004. © 2004 Society of Plastics Engineers.     

Inhibition effect of some polymers on the corrosion of cadmium in a hydrochloric acid solution

The effects of poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), sodium polyacrylate (NaPA), poly(ethylene glycol) (PEG), pectin (P), and carboxymethyl cellulose (CMC) on the corrosion of cadmium in a 0.5M hydrochloric acid (HCl) solution were studied with both electrochemical impedance spectroscopy and Tafel plot techniques. Measurements were carried out at cathodic, open‐circuit, and anodic potentials. All the investigated polymers had inhibitory effects on both the cathodic (except for NaPA, P, and CMC) and anodic processes, with a predominant anodic inhibiting action. However, NaPA, P, and CMC exhibited a slight cathodic inhibiting action only at higher polymer concentrations. This behavior may be attributed to the very weak adsorbability of the polymers on the cathodic sites. Because PVA and PEG had hydroxy groups, there could be bridging between the polymer and the surface, resulting in an inhibiting effect in the HCl solution. However, PVA had much greater adsorbability on the surface than PEG at the anodic potential. The adsorption of most of the polymers obeyed a Temkin adsorption isotherm, and this indicated indicating that the main process of inhibition was adsorption. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 866–871, 2003     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Effects of preparation conditions on the surface modification and performance of polyethersulfone ultrafiltration membranes

The impact that some membrane preparation steps had on ultrafiltration (UF) membrane characteristics and performance was studied. Polyethersulfone (PES) was employed as base polymer, while N‐methyl pyrrolidone (NMP) was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a nonsolvent pore‐forming additive. The manufacturing variables studied were solvent evaporation time and membrane surface modification, using a fluorine‐based copolymer referred to as surface‐modifying macromolecule (SMM). The flat sheet membranes, prepared via phase inversion, were characterized using solute transport data, X‐ray photoelectron spectroscopy (XPS), and contact angle measurements. Membrane performance was evaluated via filtration test protocol that included a 6‐day filtration of concentrated river water. The flux reduction with time was modeled using single and dual mechanisms of fouling. The pore blockage/cake filtration model described better the behavior of the permeation rate along the experiments. Increasing the solvent evaporation time decreased the size of the pores and the permeation rate. However, it did not significantly affect the removal of the organic compounds naturally present in the river water used as feed. XPS and contact angle measurements proved that the short evaporation periods did not allow enough SMM migration to the surface to provoke a significant effect on the membrane performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

DSC study of transitions involved in thermal treatment of foamable mixtures of PE and EVA copolymer with azodicarbonamide

The transitions and reactions involved in the thermal processing of binary mixtures of polyethylene and poly(ethylene‐co‐vinyl acetate) copolymers with different concentrations of a foaming agent (azodicarbonamide) were studied using differential scanning calorimetry (DSC). The effect of ZnO as a kicker also was discussed. The temperature at the maximum rate and the heat evolved were measured for all the processes—melting, transitions, and reactions—all the mixtures prepared were measured and compared. Azodicarbonamide decomposed differently depending on the polymeric matrix. These data can be very useful for the plastic processing industry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2015–2025, 2006     

Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

Physical properties of polycaproamide/cationic dyeable poly(ethylene terephthalate) polyblended fibers

Polycaproamide (PCA) and cationic dyeable poly(ethylene terephthalate) (CDP) polymers were blended mechanically (in ratios of 75/25, 50/50, and 25/75) in a melt twin‐screw extruder to prepare three PCA/CDP polyblended materials. The blends of PCA and CDP were spun into fibers. The molar ratio of dimethyl 5‐sulfoisophthalate sodium salt for CDP was 2%. This study investigated the physical properties of PCA/CDP polyblended fibers with nuclear magnetic resonance, gel permeation chromatography, gas chromatography, potentiometer, differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), extension stress–strain measurements, density gradient analysis, and rheometry. The experimental results of DSC proved that PCA and CDP formed an immiscible system. In an SEM image of a 50/50 PCA/CDP blend, the morphological aggregation of a larger size, from 3 to 5 μm in diameter, was observed. The rheological behavior of the PCA/CDP polyblended materials exhibited negative‐deviation blends, and the 50/50 blend of the PCA/CDP polyblended fibers showed a minimum tenacity value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1710–1715, 2004