Rheological Properties of Different Film Blowing Polyethylene Samples Under Shear and Elongational Flow

Summary: The rheological behavior of polyethylenes is mainly dominated by the molecular weight, the molecular weight distribution and by the type, the amount and the distribution of the chain branches. In this work a linear metallocene catalyzed polyethylene (m‐PE), a branched metallocene catalyzed polyethylene (m‐bPE), a conventional linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) have been investigated in order to compare their rheological behavior in shear and in elongational flow. The four samples have similar melt flow index and in particular a value typical of film blowing grade. The melt viscosity has been studied both in shear and in isothermal and non‐isothermal elongational flow. The most important features of the results are that in shear flow the m‐PE sample shows less pronounced non Newtonian behavior while in the elongational flow the behavior of m‐PE is very similar to that of the linear low density polyethylene: the narrower molecular weight distribution and the better homogeneity of the branching distribution are reasonably responsible for this behavior. Of course the most pronounced non‐linear behavior is shown, as expected, by the LDPE sample and by the branched metallocene sample. This similar behavior has to be attributed to the presence of branching. Similar comments hold in non‐isothermal elongational flow; the LDPE sample shows the highest values of the melt strength and the other two samples show very similar values. As for the breaking stretching ratio the opposite is true for LDPE while m‐PE and LLDPE show higher values. The transient isothermal elongational viscosity curves show that the branched samples show a strain hardening effect, while LLDPE and m‐PE samples present a linear behavior.

Dimensionless flow curves of different polyethylene samples.     

Catalyst pore plugging effects on hydrocracking reactions in an Ebullated bed reactor operation

This paper analyzes the deactivation effects of NiMo/Al₂O₃ catalyst during the operation in an Ebullated bed reactor for Heavy residue hydrocracking. The spent catalysts were characterized by chemical analysis, ¹³C NMR, ESM, DRX, and by using thermal programmed oxidation and diffusion studies in a shallow bed micro-reactor. The deactivations were performed in a 5 l continuously stirred tank reactor, while the spent catalysts were tested in a 0.05 l micro-reactor. The study focused on determining the properties of the external layer of the catalyst and on evaluating the internal coke and metal deposition. The results indicated that initial deactivation is mainly due to coke depositions, while its impact on mass transfer reaction control depends on temperature. In long-term deactivation, the metal deposition plays a more important role in blocking the internal micro- and meso-structures and in building up the external layer of the pellets.     

High Pressure Conductivity and Photoconductivity of Polyveratrole

Summary Electropolymerization of o-(CH₃O)₂C₆H₄ (Veratrole) in dry acetonitrile/tetrabutylammonium tetrafluoroborate at platinum electrode, yields a green polymeric conducting solid. As the pressure is increased, the material becomes more conductive, but sharp changes towards lower conductivity occur at 4.2 and 6.2 metric tons pressure, probably due to phase transitions. The photoconductivity shows an exponential increase as temperature is increased, but it shows reversible changes at 200 K, 225 K and 250 K during slow warming, also attributable to phase transitions. Photoconductivity of Polyveratrole increases with the radiation frequency, being higher under blue light than under red of infrared radiation and there is a linear increase of photoconductivity with radiation density. Conductivity transients show that the conductivity increases exponentially with time to the saturation point within few minutes, and it also decreases exponentially when the light is turned off and the circuit is open. This behaviour can be explained by formation and encounter of electron and hole as current carriers. A preliminary study indicates a piezoelectric effect for the material. absorption spectroscopy allowed the measurements of the material band gap.     

The ring transformations of 1,2,3,4-diepoxybutane (2,2′-bioxirane) catalysed by various aluminosilicates

The transformations of a molecule containing two adjacent epoxide rings, 2,2-bioxirane that is, were studied over various acidic aluminosilicates (HZSM-5, HY-FAU, AlMCM-41), for the first time, In the 373–473 K temperature range, in a pulse reactor, a ring-opening–ring-enlargment reaction producing furan only occured over the zeolites and it was the predominant reaction on AlMCM-41 as well. The driving force of this transformation route is water formation via elimination from 2,2-bioxirane. Suprising is the lack of the mono- or dialdehyde, the would-be products of the cleavage of the sterically more hindered C–O bonds – an acid-catalysed reaction typical for alkyl-substituted oxiranes.     

The effect of supercooling on crystallization of cocoa butter-vegetable oil blends

The solid fat content (SFC), Avrami index (n), crystallization rate (z), fractal dimension (D), and the pre-exponential term [log(γ)] were determined in blends of cocoa butter (CB) with canola oil or soybean oil crystallized at temperatures (T _Cr) between 9.5 and 13.5°C. The relationship of these parameters with the elasticity (G′) and yield stress (σ^*) values of the crystallized blends was investigated, considering the equilibrium melting temperature (T _M ^o) and the supercooling (i.e., T _Cr ^o−T _M ^o) present in the blends. In general, supercooling was higher in the CB/soybean oil blend [T _M ^o=65.8°C (±3.0°C)] than in the CB/canola oil blend [T _M ^o=33.7°C (±4.9°C)]. Therefore, under similar T _Cr values, higher SFC and z values (P<0.05) were obtained with the CB/soybean oil blend. However, independent of T _Cr TAG followed a spherulitic crystal growth mechanism in both blends. Supercooling calculated with melting temperatures from DSC thermograms explained the SFC and z behavior just within each blend. However, supercooling calculated with T _M ^o explained both the SFC and z behavior within each blend and between the blends. Thus, independent of the blend used, SFC described the behavior of G′_eq and σ^* and pointed out the presence of two supercooling regions. In the lower supercooling region, G′_eq and σ^* decreased as SFC increased between 20 and 23%. In this region, the crystal network structures were formed by a mixture of small β′ crystals and large β crystals. In contrast, in the higher supercooling region (24 to 27% SFC), G′_eq and σ^* had a direct relationship with SFC, and the crystal network structure was formed mainly by small β′ crystals. However, we could not find a particular relationship that described the overall behavior of G′_eq and σ^* as a function of D and independent of the system investigated.     

Evaluation of vitamin E by HPLC in a variety of olive-based foodstuffs

A survey of vitamin E levels in a wide variety of olive-based foodstuffs was conducted. Vitamin E was determined by normal-phase HPLC. The only form of vitamin E found in all commercial presentations of table olives was α-tocopherol, with an average content of 3.1 mg/100 g edible portion. A very low content (<0.4 mg/100 g edible portion) of γ-tocopherol was found in most of the samples analyzed. The main sources of variation of vitamin E were olive cultivars and commercial presentations. Processing type (Spanish style green olives, directly brined olives, ripe olives) had a limited influence. Irrespective of the elaboration style, the Gordal cultivar was the poorest with respect to the vitamin E content. On the other hand, all commercial presentations based on the Hojiblanca cultivar had high contents of vitamin E. The results of this study may be used by the industry for requirements of nutritional labeling or by nutritionists to estimate vitamin E intakes in diets that include table olives.     

Aromatization of n-hexane on Mo2C catalysts

The deposition-precipitation method was used to prepare gold catalysts based on different supports. Their catalytic activities for combustion of carbon monoxide (CO) and formaldehyde (HCHO) were investigated. All these catalysts showed good activity for the two reactions and the Au/CeO₂-a catalyst exhibited the highest activity for the two reactions. Furthermore, catalysts derived from the as-precipitate hydroxides exhibited higher activity than that from corresponding oxide supports. The BET, XRD, TEM and XPS were carried out. The results indicated that the gold dispersed more homogeneous on the as-precipitate hydroxide supports than that on the corresponding oxide supports.     

Perfectly Wetting Mixtures of Surfactants from Renewable Resources: The Interaction and Synergistic Effects on Adsorption and Micellization

This paper presents a study of the surface properties of mixtures of surfactants originating from renewable sources, i.e., alkylpolyglucoside (APG), ethoxylated fatty alcohol (AE), and sodium soap (Na soap). The main objective was to optimize the surfactant ratio which produces the highest wetting properties during the analysis of the solution of the individual surfactants, two- and three-component mixtures, and at different pH values. The results showed the existence of a synergistic effect in lowering the interfacial tension, critical micelle concentration and the formation of mixed micelles in selected solutions. We found that best wetting properties were measured for the binary AE:APG mixtures. It has been demonstrated that slightly lower contact angles values were observed on Teflon and glass surfaces for the AE:APG:soap mixtures but the results were obtained for higher concentration of the components. In addition, all studied solutions have very good surface properties in acidic, basic and neural media. However, the AE:soap (molar ratio of 1:2), AE:APG (2:1) and AE:APG:soap (1:1:1) compositions improved their wetting power at pH 7 on the aluminium and glass surfaces, as compared to solutions at other pH values tested (selected Θ values close to zero—perfectly wetting liquids). All described effects detected would allow less surfactant to be used to achieve the maximum capacity of washing, wetting or solubilizing while minimizing costs and demonstrating environmental care.     

Chemical Composition and Physical Properties of High Oleic Safflower Oils (Carthamus tinctorius,Var. CW88-OL and CW99-OL)

Chemical composition and physical properties of CW88‐OL and CW99‐OL cultivars of high oleic safflower seeds and their hexane‐extracted oils were determined. Dry‐based seed composition of CW88‐OL and CW99‐OL was: moisture = 4.29 and 4.23 %, oil = 42.29 and 46.44 %, Crude protein = 20.94 and 16.41 %, neutral detergent fiber = 28.11 and 28.49 %, ash = 1.55 and 2.01 %, phosphorus content = 2033 and 3995 mg/kg, respectively. Major fatty acids in oils were ~78 % oleic (O), ~13 % linoleic (L), ~5 % palmitic (P) and ~2 % stearic (St) acids, for both cultivars. The main triacylglycerols were OOO (~50 %), OOL (~20 %), SOL + OPO (~10 %), and LLP (~5 %). The oil composition of CW88‐OL and CW99‐OL in main minor components was: α‐tocopherol = 582 and 551 mg/kg, total sterols = 3996 and 3362 mg/kg, phospholipids = 22 and 21 mg/kg and wax content = 70 and 74 mg/kg. For both cultivars, density and viscosity of the oils between 25 and 55 °C varied from 903.4 to 912.6 kg/m³ and 63 to 23 mPa.s showing linear and exponential behaviors, respectively. The refractive index was 1.4694. The CIELab color parameters were: 89.69 and 89.53 (L*), ?3.72 and ?3.07 (a*), and 47.28 and 47.78 (b*) (CW88‐OL and CW99‐OL, respectively). Thus, the high oil content of the seeds and nutritional quality of the oil accompanied by low levels of waxes and phospholipids makes the cultivars studied promising for producers and consumers.     

Polyurethane/Polylactide-Based Electrospun Nonwovens as Carriers for Human Adipose-Derived Stromal Stem Cells and Chondrogenic Progenitor Cells

Articular cartilage dysfunctions are major cause of pain and disability and lead to serious health complications. Cell-based therapies are proposed as treatment methods for cartilage regeneration. In this study, we proposed polyurethane/poly(L-lactide-co-D, L-lactide)-based electrospun nonwovens as carriers for the delivery of human adipose-derived stromal stem cells. We found that 6:4 and 8:2 polyurethane/poly(L-lactide-co-D, L-lactide) initially enhance proliferative rate of human adipose-derived stromal stem cells, shorten their population doubling time, promote creation of functional chondrogenic nodules during chondrogenic differentiation, improve the collagen-2-to-collagen-1 protein ratio, and upregulate the expression of collagen-2 and aggrecan genes.