Rheological properties of poly(lactic acid) based nanocomposites: Effects of different organoclay modifiers and compatibilizers

Poly(lactic acid) (PLA) nanocomposites containing five types of organically modified, layered silicates and two elastomeric compatibilizers, namely ethylene‐glycidyl methacrylate (E‐GMA) and ethylene‐butyl acrylate‐maleic anhydride (E‐BA‐MAH), were prepared using a twin screw extruder. The morphologies of the nanocomposites were determined by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), and the rheological properties of the melts were measured using small‐amplitude oscillatory shear. XRD revealed that the addition of E‐GMA to the binary nanocomposites resulted in higher compatibility between the organoclay nanoplatelets and the polymer matrix. TEM showed that all of the nanocomposites contained mixed dispersed structures, involving tactoids of various sizes, as well as intercalated and exfoliated organoclay layers. Rheological properties were found to be affected by the differences in the compatibility between the organoclays and the polymer matrix, and by the addition of the compatibilizer. Organoclay types that resulted in high level of dispersion exhibited higher values of complex viscosity compared to that of neat PLA. The addition of E‐GMA introduced a solid‐like rheological behavior at low frequencies. All of the nanocomposites had similar rheological behavior at high frequencies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42915.     

Physical aging in particulate-filled composites with an amorphous glassy matrix

Physical aging was studied on particulate -filled glassy network polymers by means of mechanical -dilatational, differential scanning calorimetry (DSC) and density measurements on specimens that were aged at room temperature. The composites aged for 0.5 day fractured in a brittle manner at a constant ultimate stress, which is close to the tensile strength of the unfilled material, regardless of the filler content and the presence of a coupling agent. This type of mechanical behavior is caused by the compressive residual stresses that are present due to curing and differential thermal shrinkage. As aging takes place, the compressive residual stresses are relieved; as a result the ultimate tensile strengths of the composites decrease. The 120 -day -old untreated glass bead containing composites exhibited dilatation and yield in mechanical -dilatational testing. This type of behavior is described as “having no adhesion” between the filler and the matrix. The 120 -day -old composites with coupling agent -treated glass beads fractured at a tensile stress which is equal to 1/1.6 the tensile strength of the unfilled material. These materials did not exhibit dilatation and yield in mechanical -dilatational testing. Density and DSC data indicate densification and enthalpy relaxation upon again and support the hypothesis presented for the observed change in the mechanical -dilatational behavior.     

Effects of nucleating agent and processing conditions on the mechanical,thermal, and optical properties of biaxially oriented polypropylene films

The effects of nucleating agent, temperature of crystallization, and degree of machine direction (MD) orientation on the mechanical, optical, and thermal properties of biaxially oriented polypropylene (BOPP) films were investigated. Addition of nucleating agent improved only the initial tear resistance in the MD; however, the other mechanical and optical properties did not change appreciably. In the set of experiments in which the crystallization temperature was increased, the degree of crystallinity also increased. Thus, Young's modulus, yield stress, and tensile strength increased in both directions with higher degree of crystallinity. The yield strain did not change significantly, but the strain at break was higher. Although the initial tear resistance was smaller in both directions with increasing crystallization temperature, the tear propagation resistance did not change. In this case, haze and diffuse transmittance were slightly higher, but the total transmittance was constant. In the set of experiments in which the machine direction orientation was increased, the degree of crystallinity also became higher. Owing to the effects of higher crystallinity and higher MD orientation, the modulus, yield stress, and tensile strength increased, but the yield strain and tear propagation resistance did not significantly change in both directions.     

Doxorubicin-Induced Autophagolysosome Formation Is Partly Prevented by Mitochondrial ROS Elimination in DOX-Resistant Breast Cancer Cells

Since its discovery, mitophagy has been viewed as a protective mechanism used by cancer cells to prevent the induction of mitochondrial apoptosis. Most cancer treatments directly or indirectly cause mitochondrial dysfunction in order to trigger signals for cell death. Elimination of these dysfunctional mitochondria by mitophagy could thus prevent the initiation of the apoptotic cascade. In breast cancer patients, resistance to doxorubicin (DOX), one of the most widely used cancer drugs, is an important cause of poor clinical outcomes. However, the role played by mitophagy in the context of DOX resistance in breast cancer cells is not well understood. We therefore tried to determine whether an increase in mitophagic flux was associated with the resistance of breast cancer cells to DOX. Our first objective was to explore whether DOX-resistant breast cancer cells were characterized by conditions that favor mitophagy induction. We next tried to determine whether mitophagic flux was increased in DOX-resistant cells in response to DOX treatment. For this purpose, the parental (MCF-7) and DOX-resistant (MCF-7dox) breast cancer cell lines were used. Our results show that mitochondrial reactive oxygen species (ROS) production and hypoxia-inducible factor-1 alpha (HIF-1 alpha) expression are higher in MCF-7dox in a basal condition compared to MCF-7, suggesting DOX-resistant breast cancer cells are prone to stimuli to induce a mitophagy-related event. Our results also showed that, in response to DOX, autophagolysosome formation is induced in DOX-resistant breast cancer cells. This mitophagic step following DOX treatment seems to be partly due to mitochondrial ROS production as autophagolysosome formation is moderately decreased by the mitochondrial antioxidant mitoTEMPO.     

Dilatancy of concentrated suspensions with Newtonian matrices

Suspensions filled close to their maximum packing fraction present special challenges in their processing and in their rheological characterization. In this report, the literature in the area of dilatancy of concentrated suspensions is reviewed. Furthermore, the shear viscosity of a Newtonian polymeric liquid filled with 60 vol. percent of ammonium sulfate has been investigated. Both capillary and parallel disk torsional flows, were employed, spanning three decades in shear stress. Upon correction for slip, the suspension exhibited shear thinning at low shear stresses and shear thickening at higher shear stresses. Above a critical wall shear stress, the shear viscosity of the suspension increased unboundedly and the flow became pluglike with apparent slip at the wall. These findings have important ramifications in the processing of composites from such concentrated suspensions.     

Effect of different types of organoclays and compatibilizers on the properties of polystyrene‐based nanocomposites

Polystyrene/organoclay nanocomposites were prepared by melt intercalation in the presence of elastomeric impact modifiers. Three different types of organically modified montmorillonites; Cloisite® 30B, 15A, and 25A, were used as reinforcement, whereas poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS‐g‐MA) and poly(ethylene‐b‐butyl acrylate‐b‐glycidyl methacrylate) (E‐BA‐GMA) elastomeric materials were introduced to act as impact modifier. Owing to its single aliphatic tail on its modifier and absence of hydroxyl groups, Cloisite® 25A displayed the best dispersion in the polystyrene matrix, and mostly delaminated silicate layers were obtained in the presence of SEBS‐g‐MA. This was attributed to the higher viscosity of SEBS‐g‐MA compared with both E‐BA‐GMA and poly(styrene‐co‐vinyloxazolin) (PS). In addition, the compatibility between SEBS‐g‐MA and PS was found to be better in comparison to the compatibility between E‐BA‐GMA and PS owing to the soluble part of SEBS‐g‐MA in PS. The clay particles were observed to be located mostly in the dispersed phase leading to larger elastomeric domains compared with binary PS/elastomer blends. The enlargement of the elastomeric domains resulted in higher impact strength values in the presence of organoclay. Good dispersion of Cloisite® 25A in PS/SEBS‐g‐MA blends enhanced the tensile properties of this nanocomposite produced. It was observed that the change in the strength and stiffness of the ternary nanocomposites mostly depend on the type of the elastomeric material. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Viscosity and die swell of acrylonitrile-butadiene-styrene filled with glass beads and glass fibers

Shear viscosity and die swell ratio of acrylonitrile-butadiene-styrene filled with glass beads and glass fibers were measured. The relative viscosity of the composites increased with filler content, but decreased with shear rate. At low shear rates, fiber filled systems had higher relative viscosities than bead filled systems. At high shear rates, the opposite was observed. The die swell ratio of the unfilled material increased linearly with the logarithm of the shear rate. Systems highly filled with glass beads or fibers showed a maximum in the die swell ratio at medium shear rates. The magnitude of the maximum in the die swell ratio increased with the filler content and the die length, up to a certain length, in a series of dies that had the same radius. The presence of a maximum in the die swell ratio of the filled melts is explained by an order-disorder phenomenon observed earlier by Wu.     

Improving functionality of whole egg powder by the addition of gelatine, lactose, and pullulan

The addition of gelatine (G), lactose (L), pullulan (P), and their mixtures at equal ratios (gelatine + lactose [GL] and gelatin + pullulan [GP]) to whole egg prior to drying was studied. Their effects on the functional properties (emulsion and gelling ability, water holding capacity of gel, foaming, color) and soluble protein content of spray dried egg powder during the 6 mo of storage at 20 °C and 50% relative humidity were investigated. It was demonstrated that the emulsion and foaming stability, water holding capacity of gel, and color change were significantly affected by the storage time, whereas storage time did not affect the strength of gel texture prepared by egg powders. Gelatine and pullulan improved the foaming stability and water holding capacity. Lactose caused a decrease in emulsion and foaming stability values. The maximum color change was observed for the plain egg powder, showing that mixing whole egg with carbohydrate- and/or protein-based additives before the drying process preserved the color of egg powder. Adding carbohydrate and/or protein caused significant changes in functional properties of egg powder.     

Occurrence of disinfection by-products in low DOC surface waters in Turkey

A total of 29 surface waters from different regions of Turkey were sampled once a month during 2004. Filtered raw water samples were characterized, chlorinated and the concentrations of disinfection by-products (DBPs) were measured. All waters were low in DOC ranging from 0.91 to 4.42 mg/L. The range of annual average trihalomethanes (THMs) and haloacetic acids (HAAs) concentrations in all waters was 21-189 and 18-149mug/L, respectively. Total mass contributions of halides in THMs and HAAs to absorbable organic halides (AOX) ranged between 10 and 56% in all waters on annual average basis, indicating that significant amounts of other DBPs are being formed in the majority of the tested waters. A strong linear correlation was obtained between the concentrations of THMs and HAAs. Rather poor correlations were found for THMs-AOX and HAAs-AOX levels. For both THMs and HAAs, chlorinated species dominated over brominated ones since the majority of water sources had very low bromide levels. While chloroform and trichloroacetic acid were the major THM and HAA compounds, respectively; the extent of formation and speciation of DBPs varied greatly by season and water source. No consistent general trends were observed in terms of seasonal variations in DBP levels, suggesting that the characteristics of NOM moieties and their chlorine reactivity vary by season in almost all waters tested.     

Prototypes for building applications based on thermoplastic composites containing mixed waste plastics

Automotive shredder residue (ASR) and a complex residue obtained as a by‐product in the tertiary recycling of nylon‐6 fibers from used carpets were evaluated as potential additives in thermoplastic composites to be used for building applications. Prototype blocks were prepared by the “intrusion” process using various ratios of the waste streams and low‐density polyethylene (LDPE) in the absence of compatibilizers. Hence, product morphologies and corresponding properties were largely controlled through processing. They were evaluated for their short‐term and longterm mechanical properties, flammability, thermal conductivity, and heavy‐metal and total organic carbon leaching characteristics. Encapsulation of the waste feedstock by LDPE during molding in a single‐screw extruder significantly reduced the leachable content. In an effort to further reduce the leachable content, the mixtures were processed in two stages by precompounding in adevolatilizing twin‐screw extruder prior to molding. In comparison to the as‐received wastes, improved homogenization decreased the leachable heavy‐metal content by at least 98%. The carpet residue feedstock consisting of polypropylene, styrene‐butadiene rubber and calcium carbonate appears to be an attractive low‐cost, high‐volume material with consistent properties and could be used as filler in thermoplastic composites. Comparison of their performance characteristics suggested that the carpet residue composites would be favored versus ASR composites as replacement of the wood thermal barrier components in a novel steel‐based stud assembly.