Effects of mixing protocols on impact modified poly(lactic acid) layered silicate nanocomposites

Poly(lactic acid)/2 wt % organomodified montmorillonite (PLA/OMMT) was toughened by an ethylene‐methyl acrylate‐glycidyl methacrylate (E‐MA‐GMA) rubber. The ternary nanocomposites were prepared by melt compounding in a twin screw extruder using four different addition protocols of the components of the nanocomposite and varying the rubber content in the range of 5–20 wt %. It was found that both clay dispersion and morphology were influenced by the blending method as detected by X‐ray diffraction (XRD) and observed by TEM and scanning electron microscopy (SEM). The XRD results, which were also confirmed by TEM observations, demonstrated that the OMMT dispersed better in PLA than in E‐MA‐GMA. All formulations exhibited intercalated/partially exfoliated structure with the best clay dispersion achieved when the clay was first mixed with PLA before the rubber was added. According to SEM, the blends were immiscible and exhibited fine dispersion of the rubber in the PLA with differences in the mean particle sizes that depended on the addition order. Balanced stiffness‐toughness was observed at 10 wt % rubber content in the compounds without significant sacrifice of the strength. High impact toughness was attained when PLA was first mixed with the clay before the rubber was added, and the highest tensile toughness was obtained when PLA was first compounded with the rubber, and then clay was incorporated into the mixture. Thermal characterization by DSC confirmed the immiscibility of the blends, but in general, the thermal parameters and the degree of crystallinity of the PLA were not affected by the preparation procedure. Both the clay and the rubber decreased the crystallization temperature of the PLA by acting as nucleating agents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41518.     

Dynamic risk analysis using alarm databases to improve process safety and product quality: Part I—Data compaction

In most industrial processes, vast amounts of data are recorded through their distributed control systems (DCSs) and emergency shutdown (ESD) systems. This two‐part article presents a dynamic risk analysis methodology that uses alarm databases to improve process safety and product quality. The methodology consists of three steps: (i) tracking of abnormal events over an extended period of time, (ii) event‐tree and set‐theoretic formulations to compact the abnormal‐event data, and (iii) Bayesian analysis to calculate the likelihood of the occurrence of incidents. Steps (i) and (ii) are presented in Part I and step (iii) in Part II. The event‐trees and set‐theoretic formulations allow compaction of massive numbers (millions) of abnormal events. For each abnormal event, associated with a process or quality variable, its path through the safety or quality systems designed to return its variable to the normal operation range is recorded. Event trees are prepared to record the successes and failures of each safety or quality system as it acts on each abnormal event. Over several months of operation, on the order of 10⁶ paths through event trees are stored. The new set‐theoretic structure condenses the paths to a single compact data record, leading to significant improvement in the efficiency of the probabilistic calculations and permitting Bayesian analysis of large alarm databases in real time. As a case study, steps (i) and (ii) are applied to an industrial, fluidized‐catalytic‐cracker. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Characteristics of impact modified polystyrene/organoclay nanocomposites

The poor impact resistance of Polystyrene (PS) was enhanced by the addition of elastomeric material, SEBS‐g‐MA. To prevent the reduction in strength and stiffness, organoclay Cloisite® 25A was used as filler and introduced into the matrix by a corotating twin screw extruder. Throughout the study, the clay content was kept at 2 wt%, whereas the content of SEBS‐g‐MA was varied between 5 and 40 wt%. It was found that Cloisite® 25A displays well dispersion in the ternary nanocomposites and the degree of dispersion increases with the elastomer content. The elastomeric phase has a greater viscosity than pure PS. Thus, as expected, at low elastomer contents, it forms the dispersed phase in the matrix as droplets. Transmission electron microscopy results show that the clay layers reside at the interphase between PS and elastomer and also inside the elastomeric phase. Owing to the location of the clay particles, the average elastomer domain size in ternary nanocomposites are found to be greater than that in the relative binary blends of PS‐(SEBS‐g‐MA). Moreover, with the organoclay addition, phase inversion point shifts to lower elastomer contents. The mechanical test results showed that the nanocomposites containing 15 and 20 wt% SEBS‐g‐MA have the optimum average domain size that results in high‐impact strength values without deteriorating the tensile properties. POLYM. COMPOS., 31:1853–1861, 2010. © 2010 Society of Plastics Engineers.     

Polyamide 66 binary and ternary nanocomposites: Mechanical and morphological properties

Polyamide 66 (PA 66)/impact modifier blends and polyamide/organoclay binary and PA 66/organoclay/impact modifier ternary nanocomposites were prepared by the melt‐compounding method, and the effects of the mixing sequences on the morphology and mechanical and flow properties were investigated. Lotader AX8840 and Lotader AX8900 were used as impact modifiers. The concentrations of the impact modifiers and the organoclay (Cloisite 25A) were maintained at 2 and 5 wt %, respectively. Both the binary and ternary nanocomposites displayed high tensile strength and Young's modulus values compared to the PA 66/impact modifier blends. Decreases occurred in the strength and stiffness of the binary nanocomposites upon incorporation of the elastomeric materials into the polymeric matrix. In general, the mixing sequence in which all three ingredients were added simultaneously and extruded twice (the All‐S mixing sequence) exhibited the most enhanced mechanical properties in comparison with the mixing sequences in which two of the components were extruded in the first extrusion step and the third ingredient was added in the second extrusion step. The mechanical test results were in accordance with the organoclay dispersion. The impact strength was highly affected by the elastomeric domain sizes, interdomain distances, interfacial interactions, and organoclay delamination. The smallest elastomeric domain size was obtained for the All‐S mixing sequence, whereas the elastomeric domain sizes of the other mixing sequences were quite close to each other. Drastic variations were not observed between the melt viscosities of the ternary nanocomposites prepared with different mixing sequences. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reactive extrusion of poly(ethylene terephthalate)–(ethylene/methyl acrylate/glycidyl methacrylate)–organoclay nanocomposites

This study was conducted to investigate the effects of component concentrations and addition order of the components on the final properties of ternary nanocomposites composed of poly(ethylene terephthalate), organoclay, and an ethylene–methyl acrylate–glycidyl methacrylate (E‐MA‐GMA) terpolymer acting as an impact modifier for PET. In this context, first, the optimum amount of the impact modifier was determined by melt compounding binary PET‐terpolymer blends in a corotating twin‐screw extruder. The amount of the impact modifier (5 wt%) resulting in the highest Young's modulus and moderate elongation at break was selected owing to its balanced mechanical properties. Thereafter, by using 5 wt% terpolymer content, the effects of organically modified clay concentration and addition order of the components on the properties of ternary nanocomposites were systematically investigated. Mechanical testing revealed that different addition orders of the materials significantly affected the mechanical properties. Among the investigated addition orders, the best sequence of component addition (PI‐C) was the one in which poly(ethylene terephthalate) was first compounded with E‐MA‐GMA. Later, this mixture was compounded with the organoclay in the subsequent run. In X‐ray diffraction analysis, extensive layer separation associated with delamination of the original clay structure occurred in PI‐C and CI‐P (Clay + Impact Modifier followed by PET) sequences with both 1 and 3 wt% clay contents. X‐ray diffraction patterns showed that at these conditions exfoliated structures resulted as indicated by the disappearance of any peaks due to the diffraction within the consecutive clay layers. POLYM. COMPOS., 28:251–258, 2007. © Society of Plastic Engineers     

An intrinsic time to fracture criterion for amorphous polymers

An energy probability theory of global fracture is formulated using the notion of intrinsic time starting with first principles. Comparisons are made between the theory and experiments on Styrene-Butadiene Rubber, thus explaining various aspects of failure.It is proposed that fracture occurs as a result of accumulation of broken carbon-carbon bonds. When a critical concentration of broken bonds is reached, catastrophic failure begins and the specimen fractures. It is assumed that the probability of fracture of a single carbon-carbon bond is determined by the energy content of the bond. Non-uniform distribution of the free energy of the specimen among bonds is taken into account by means of an exponential distribution function. The intrinsic time measure pertinent to the constitutive equation of the material is used as the time measure of fracture. This allows use of the time-temperature shift principle, applicable to fracture of polymers, and enables the prediction of lifetimes in high strain rate conditions.Finally the theory predicts correctly that, at constant amplitudes, the number of cycles to failure at low frequencies is directly proportional to the frequency and is independent of the latter at high frequencies.     

Membrane based strategies for the pre-treatment of acid dye bath wastewaters

This paper, as part of a study carried out for the recovery of the acid dye bath wastewaters of a carpet manufacturing industry by membrane processes, describes the evaluation of alternative strategies for the pre-treatment of acid dye bath wastewaters. Dead-end microfiltration (MF) simulating sand filtration with MF media having pore sizes of 2.5, 1.0, 0.45 and 0.2 microm and ultrafiltration (UF) with an UF membrane having a molecular weight cut off (MWCO) of 50,000 Da were tested in single and sequential stages in order to achieve the best treatment efficiency. Four alternative process trains were tested; single MF, sequential MF, single UF, and MF followed by UF. For both MF and UF, application of sequential filtration did not provide any significant benefit over single processes. In addition, chemical oxygen demand (COD) removal performance of all the alternative processes was similar where the highest removal was only 5%. On the other hand, color removals were much better; ranging from 15 to 100%, even with single MF. Comparison of all the process alternatives revealed that, single MF (0.45 microm), as the simplest process, is the most suitable pre-treatment method for the acid dye bath wastewaters.