Prerparation of graphene oxide-poly(methyl methacrylate) nanocompposites by a precipitation polymerization process and their dielectric and rheological characterization

The graphene sheet, a flat monolayer composed of sp2-bonded carbon atoms packed into a two-dimensional honeycomb structure, has attracted a tremendous attention due to its extraordinary electrical, thermal, and mechanical properties. Graphene nanosheets–poly(methyl methacrylate) GN/PMMA nanocomposites were prepared via a precipitation polymerization process in a water/methanol mixture and thermal or chemical reduction of graphene oxide (GO). Scanning electron and transmission electron microscopies confirmed that the precipitate consists of polymer particles (<1μm) surrounded by the GO sheets. The GO sheets acts as a surfactant and adsorbs on the interface between polymerized PMMA particles and solvent mixture. Parallel dielectric and rheological characterization demonstrated that the thermal reduction is a quite fast process without significant degradation of the polymer. In addition, the main increase in electrical conductivity occurred during the first minutes of the thermal treatment but continued for about 30 min. The absence of dramatic change in the storage modulus confirmed that the increase in conductivity was not due to alteration of the particle dispersion. The addition of GO sheets had a dramatic influence on the glass transition (Tg) temperature of PMMA with an increase of 8 °C at only 0.2 wt %. This Tg increase has been attributed to the restricted mobility of PMMA chains which have been grafted onto the graphene surfaces during the in-situ polymerization. However, at GO content higher than 0.7 wt %, the glass transition decreases. This drop may be attributed to the increase in the number of stacked graphene layers. The obtained GN/PMMA composites not only have enhanced mechanical properties but also achieved electrical conductivity higher than 10 −2 S/m at 0.4 wt % of GO. The study should open up new opportunities in the design of GN-based polymer nanocomposites

Stabilization of Oil-in-Water Emulsions with Noninterfacially Adsorbed Particles

Classical (surfactant stabilized) and Pickering (particle stabilized) type emulsions have been widely studied to elucidate the mechanisms by which emulsion stabilization is achieved. In Pickering emulsions, a key defining factor is that the stabilizing particles reside at the liquid–liquid interface providing a mechanical barrier to droplet coalescence. This interfacial adsorption is achieved through the use of nanoparticles that are partially wet by both liquid phases, often through covalent surface modification of or surfactant adsorption to the nanoparticle surfaces. Herein, we demonstrate particle-induced stabilization of an oil-in-water emulsion with fully water wet nanoparticles (no interfacial adsorption) via synergistic interaction with low concentrations of surfactants. Laser scanning confocal microscopy analysis allows for unique and vital insights into the properties of these emulsions via both three-dimensional imaging and real-time monitoring of particle dynamics at the oil–water interface. Investigation of these “non-Pickering” particle stabilized emulsions suggests that the nonadsorbed particles impart stability to the emulsion primarily via entropic forces imparted by the accumulation of silica nanoparticles in the coherent phase between dispersed oil droplets

Fluorescent polycatecholamine nanostructures as a versatile probe for multiphase systems

Shape and size controlled nanostructures are critical for nanotechnology and have versatile applications in understanding interfacial phenomena of various multi-phase systems. Facile synthesis of fluorescent nanostructures remains a challenge from conventional precursors. In this study, bio-inspired catecholamines, dopamine (DA), epinephrine (EP) and levodopa (LDA), were used as precursors and fluorescent nanostructures were synthesized via a simple one pot method in a water–alcohol mixture under alkaline conditions. DA and EP formed fluorescent spheres and petal shaped structures respectively over a broad spectrum excitation wavelength, whereas LDA did not form any particular structure. However, the polyepinephrine (PEP) micropetals were formed by weaker interactions as compared to covalently linked polydopamine (PDA) nanospheres, as revealed by NMR studies. Application of these fluorescent structures was illustrated by their adsorption behavior at the oil/water interface using laser scanning confocal microscopy. Interestingly, PDA nanospheres showed complete coverage of the oil/water interface despite its hydrophilic nature, as compared to hydrophobic PEP micropetals which showed a transient coverage of the oil/water interface but mainly self-aggregated in the water phase. The reported unique fluorescent organic structures will play a key role in understanding various multi-phase systems used in aerospace, biomedical, electronics and energy applications.Sponsored by the Open Access Authors Fun

Controlling the Morphology of Immiscible Cocontinuous Polymer Blends via Silica Nanoparticles Jammed at the Interface

Cocontinuous polymer blends have wide applications. They can form conductive plastics with improved mechanical properties. When one phase is extracted, they yield porous polymer sheets, which can be used as filters or membrane supports. However, the cocontinuous morphology is intrinsically unstable due to coarsening during static annealing. In this study, silica nanoparticles, ∼100 nm diameter, with different wetting properties were melt compounded in polyethylene/poly­(ethylene oxide) blends. Calculated wetting coefficients of these particles match well with their phase contact angles and their locations in the blends. We demonstrated that a monolayer of particles jamming at interfaces can effectively suppress coarsening and stabilize the cocontinuous morphology. We also correlated the wettability of individual particles at interface to their coarsening suppression ability and found that the most hydrophobic silica nanoparticle is the most effective to arrest coarsening. Moreover, during annealing, we used the rheological dynamic time sweep, a facial but sensitive method, to relate the morphology change with particle dispersion on the interface. We further corroborated these measurements by scanning electron microscopy and confocal microscopy imaging

Engineering Integrity: Using text-matching software in a graduate level engineering course

Academic misconduct is an unfortunate reality for many post-secondary level educators across disciplines; however, there is currently a paucity of Canadian research on Academic Integrity (Eaton, 2018). This study describes an inter-disciplinary project to investigate the potential for text-matching software to prevent and avoid plagiarism by graduate level engineering students. Conceptual/Theoretical Framework: Our study was informed by the potential for text-matching software to help students understand and avoid plagiarism (Zaza & McKenzie, 2018) and faculty identify instances of plagiarism in an engineering course (Cooper & Bullard, 2014). Although text-matching software has been commercially available since the 1990s, its acceptance within academic contexts is uneven. Reasons for this are manifold, but the most commonly expressed concerns are about a) the punitive nature of the software use; b) the potential for it to be used as a tool for cheating students to “beat the system”, and c) privacy concerns (Savage, 2004). Methodology / Approach: In this project, approved by the institutional REB, assignments submitted in a graduate-level engineering communication course were analyzed using text-matching software, Ithenticate. The first phase of the study involved collecting baseline data from students enrolled in a graduate-level Engineering course (N=132). As per REB protocol, individual results were not shared with the professor or teaching assistants and sharing of aggregated results is not permitted until after February 15, 2019. In our presentation, we share baseline results, as well as outcomes of the second phase of the research, in which the research associate revealed the deception, explained the study, and solicited consent from students to have their next assignment harvested and analyzed. The research associate also introduced the software and provided a workshop on academic integrity including strategies for avoiding plagiarism, such as paraphrasing. Subsequent to these workshops, assignments written by consenting participants were analyzed with Ithenticate to determine whether a reduction in textual similarity occurred. Results / Findings: The results of this study indicate that text-matching software can be useful to students and educators to prevent and identify academic misconduct. This study will add to the growing body of empirical research about academic integrity in Canada and in particular, in engineering contexts

Porous Films via PE/PEO Cocontinuous Blends

The design of a porous membrane support layer derived from cocontinuous polymer blends is presented. We investigate the effect of blend composition, shear rate, residence time, and annealing time on the cocontinuous morphology of polyethylene (PE)/poly­(ethylene oxide) (PEO) blends. Porous PE sheets were generated by water extraction of PEO and used as a support layer for gas separation membranes. The PE/PEO blends using nonfunctional and maleic anhydride functional PE (PE-<i>g</i>-MA) were mixed in a batch microcompounder and in a pilot plant scale corotating twin-screw extruder. Using PE-<i>g</i>-MA resulted in pore size reduction from 10 to 2 μm and suppression of coarsening of the morphology during further annealing of the blends due to formation of PE–PEO graft copolymers. Equilibrium interfacial tension, estimated by fitting the rheology of droplet blends to the Palierne viscoelastic droplet model, was 3 and 0.4 mN/m for PE/PEO and PE-<i>g</i>-MA/PEO systems, respectively. The specific interfacial area and phase size distribution were calculated from 3D images acquired by laser scanning electron microscopy (LSCM). We prepared gas separation membranes by solvent casting an acetone solution of ionic gel into porous PE sheets and discussed the effect of type of processing, average pore size, pore size distribution, and pore wall functionality on their performance

Stabilization of PE/PEO Cocontinuous Blends by Interfacial Nanoclays

Organomodified clays are known to be effective in polymer blend compatibilization if located preferentially at the domain interfaces, but little is known regarding the origin of their localization. In this study, we investigate the effect of organomodifier, clay loading, and shear environment on the compatibilization extent in nonreactive polyethylene (LDPE)/poly­(ethylene oxide) (PEO) and reactive maleic anhydride functional polyethylene (PE-<i>g</i>-MA)/PEO polymer blends. We pose important questions: If clay is to compatibilize blends by interfacial localization, how does organomodifier affect its localization? How does an increase in clay loading affect the shape and elasticity of the interface? What is the shear intensity needed to overcome the equilibrium distribution of clays and delaminate it from the interface? We utilize laser scanning confocal microscopy and 3D image analysis to calculate characteristic phase size and gain unique insights into the connection between the clay loading and the interfacial curvature. Our experiments demonstrate that 1 wt % of interfacially localized clay is sufficient to suppress coarsening and greatly reduce phase domains. However, further increase of clay loading only saw a marginal reduction in phase size compared to 1 wt % clay loading. The interfacial curvature calculations showed that with increase in clay loadings beyond 1 wt % the shape of the interface does not change significantly; however, slight broadening of curvature distribution and increasing asymmetry are observed from 3D images. This can be attributed to the multiple layers of clay jammed at the interface at higher clay loadings. When reactive PE-<i>g</i>-MA was substituted for LDPE, graft copolymers were generated via <i>in situ</i> coupling at the interface. These copolymers combined with clay resulted in the smallest phase domains. In addition, we show that clay dispersion and localization were largely independent of shear intensity, which suggests that clay does not delaminate from the interface even in high shear environments

Coupling Particle Ordering and Spherulitic Growth for Long-Term Performance of Nanocellulose/Poly(ethylene oxide) Electrolytes

Development of lithium-ion batteries with composite solid polymer electrolytes (CPSEs) has attracted attention due to their higher energy density and improved safety compared to systems utilizing liquid electrolytes. While it is well known that the microstructure of CPSEs affects the ionic conductivity, thermal stability, and mechanical integrity/long-term stability, the bridge between the microscopic and macroscopic scales is still unclear. Herein, we present a systematic investigation of the distribution of TEMPO-oxidized cellulose nanofibrils (t-CNFs) in two different molecular weights of poly(ethylene oxide) (PEO) and its effect on Li+ ion mobility, bulk conductivity, and long-term stability. For the first time, we link local Li-ion mobility at the nanoscale level to the morphology of CPSEs defined by PEO spherulitic growth in the presence of t-CNF. In a low-MW PEO system, spherulites occupy a whole volume of the derived CPSE with t-CNF being incorporated in between lamellas, while their nuclei remain particle-free. In a high-MW PEO system, spherulites are scarce and their growth is arrested in a non-equilibrium cubic shape due to the strong t-CNF network surrounding them. Electrochemical strain microscopy and solid-state 7Li nuclear magnetic resonance spectroscopy confirm that t-CNF does not partake in Li+ ion transport regardless of its distribution within the polymer matrix. Free-standing CSPE films with low-MW PEO have higher conductivity but lack long-term stability due to the existence of uniformly distributed, particle-free, spherulite nuclei, which have very little resistance to Li dendrite growth. On the other hand, high-MW PEO has lower conductivity but demonstrates a highly stable Li cycling response for more than 1000 h at 0.2 mA/cm2 and 65 °C and more than 100 h at 85 °C. The study provides a direct link between the microscopic dynamic, Li-ion transport, bulk mechanical properties and long-term stability of the derived CPSE and, and as such, offers a pathway towards design of robust all-solid-state Li-metal batteries