Bulletin of the American Physical Society
APS March Meeting 2018
Volume 63, Number 1
Monday–Friday, March 5–9, 2018; Los Angeles, California
Session X43: Polymer Nanocomposites IV |
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Sponsoring Units: DPOLY Chair: Robert Hickey, Pennsylvania State Univ Room: LACC 503 |
Friday, March 9, 2018 8:00AM - 8:12AM |
X43.00001: Mesoporous Organosilica as Lithium Single-Ion Conducing Nanoparticle in Nanocomposite Polymer Electrolytes U Hyeok Choi, Ho Kyun Jung, Puji Handayani, Youngdo Kim We have synthesized mesoporous silica-based lithium single-ion conducting nanoparticles containing weak-binding imide (SO2NSO2CF3-) anions with lithium counterions and co-grafting solvating oligo-poly(ethylene glycol) (CH2CH2O)6-9 chains. These nanoparticles are then introduced into poly(ethylene oxide) matrix, allowing us to prepare nanocomposite polymer electrolytes. The principal focus of this presentation is on the insight about our understanding of ion and polymer dynamics of the single-ion Li conducting nanocomposite polymer electrolytes. We use various experimental methods (SAXS, FE-SEM, TEM, and BET) to check the microstructure, pore size, and surface area of the mesoporous nanoparticles. The ionic conductivity, storage module, lithium transference number of the nanocomposite polymer electrolytes are also investigated using dielectric spectroscopy, oscillatory shear, DC polarization/AC impedance. Understanding experimental observations in these materials provides useful insights for the design of single-ion conductors for energy applications. |
Friday, March 9, 2018 8:12AM - 8:24AM |
X43.00002: Elucidating the Impact of Silica Nanoparticles on Water Transport and Local Chain Relaxation Dynamics in Ionomer Nanocomposites Apoorv Balwani, Antonio Faraone, Eric Davis Nafion-silica nanocomposites (NSiNCs) have garnered interest as the proton exchange membrane in vanadium redox flow batteries as they help to combat the issue of high vanadium ion crossover, which results in a reduction of battery lifetime. To date, however, the mechanism of crossover reduction in these NSiNCs remains unclear. We expect the water-mediated ion transport to be coupled to the local chain relaxation dynamics and propose that silica nanoparticles (SiNPs) impact this interaction. To elucidate the relationship between water/ion transport and chain dynamics, we employ neutron spin echo (NSE) spectroscopy to quantify segmental relaxation dynamics and time-resolved attenuated total reflectance-Fourier transform infrared (tATR-FTIR) spectroscopy to evaluate the water sorption kinetics. Results from NSE suggest a decrease in segmental relaxation dynamics with introduction of SiNPs, while tATR-FTIR data indicate deviation from Fickian transport for all samples investigated. These sorption data were regressed to a diffusion-relaxation model to provide further insight into the effect of SiNPs on the viscoelastic properties of NSiNCs. Results from this investigation establish a basis for understanding the interplay between water/ion transport and chain dynamics in NSiNCs. |
Friday, March 9, 2018 8:24AM - 8:36AM |
X43.00003: Effect of SiO2 Nanoparticles on the Conformations of Poly(ethylene oxide) Polymer Chains Kyriakh Chrissopoulou, Helen Papananou, Spiros Anastasiadis, Anastassia Rissanou, Vagelis Harmandaris, Konstantinos Andrikopoulos, George Voyiatzis The behavior of polymers restricted in space or close to surfaces/interfaces can be very different from that in the bulk. In this work, the chain conformations in poly(ethylene oxide) / silica nanoparticles, PEO / SiO2, nanohybrids has been investigated through a combined approach that involves Fourier Transform Infrared spectroscopy (ATR-FTIR) measurements and molecular dynamics (MD) simulations. Systems with different polymer molecular weights, nanoparticle radii and concentrations have been employed to investigate the effect of the confinement on polymer conformations. Qualitatively similar behavior between experimental and simulation results is observed since in both cases an increase of gauche population for the OCCO angle is attained, in comparison to the respective of the bulk; this increase becomes larger as the degree of confinement becomes higher. On the contrary, the conformations of the C-O bond (COCC angle) seem to remain unaffected by the confinement, at least in the range of degrees of confinement covered computationally. This research has been co-financed by the General Secretariat for Research and Technology (Action KRIPIS, project AENAO, MIS: 5002556). |
Friday, March 9, 2018 8:36AM - 8:48AM |
X43.00004: Ionic depletion at the crystalline Gibbs layer of PEG-capped gold nanoparticles brushes at aqueous surfaces. David Vaknin, Honghu Zhang, Surya Mallapragada, Alex Travesset, Wenjie Wang In-situ surface sensitive X-ray diffraction and grazing incidence X-ray fluorescence spectroscopy (GIXFS) methods are combined to determine the ionic distributions across the liquid interfaces of thiolated-polyethylene-glycol capped gold nanoparticles (PEG-AuNPs) solutions. Induced by the addition of salts (i.e., Cs2SO4) to PEG-AuNPs solutions, 2D hexagonal lattices of PEG-AuNPs form spontaneously at the aqueous surfaces, as has been demonstrated by X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). By taking advantage of element specificity with GIXFS method, we find that the cation Cs+ concentration at the crystalline film is significantly reduced in parts of the PEG-AuNPs film compared to that in the bulk. |
Friday, March 9, 2018 8:48AM - 9:00AM |
X43.00005: Graphene Surface Decorated with Hybrid Perovskite Nanoparticles for Radiation Detection and Photovoltaic Applications John Murphy, Jessica Andriolo, Molly Brockway, Jack Skinner Graphene-based polymer nanocomposites are increasing more utilized for their ability to modify mechanical and opto-electronic properties of low-cost polymeric materials with relative ease. Additionally, graphene is well-suited to functionalization through chemical modification. Combination of functionalized graphene and traditional wet chemical nanoparticle synthesis methods has facilitated the creation of a whole host of surface-decorated graphene-based nanomaterials. The focus of this work is on the use of amine-functionalized graphene as a capping agent during synthesis of hybrid perovskite nanoparticles (HOIPNPs) to create graphene surface-decorated with HOIPNPs. HOIP materials have an easily tunable bandgap, ambipolar charge carrier transport, and are capable of attenuation of x-ray/gamma photons; which make them ideal candidates for solar cells and radiation detecting applications. HOIPNPs surface-decorated graphene will be dispersed into polymeric solutions to create a polymer nanocomposite. Opto-electronic properties of the nanocomposite will be evaluated using spectroscopic techniques paired with IV-sweeps. Morphology and chemical phase information will be assessed using atomic force microscopy and scanning electron microscopy. |
Friday, March 9, 2018 9:00AM - 9:12AM |
X43.00006: Using Block Copolymers as a Templating Additive to Create Ordered Polymer Nanocomposites Deborah Liu, Daniel Krogstad Polymer nanocomposites have shown incredible potential to lead to seemingly limitless innovations in a wide range of fields; however for many applications the optimal properties are only attained when the nanoparticles are well dispersed, or even ordered, within the matrix. While there has been significant progress in creating materials with an increased dispersion of nanoparticles, progress in creating bulk nanocomposites with long-range order has been slow. In this presentation, we will discuss our recent efforts in using block copolymers as an additive to promote the ordering of nanoparticles in epoxy thermosets. The addition of the block copolymers in the epoxy resin creates a gel-like structure allowing for annealing of the block copolymer ordered structure prior to crosslinking the epoxy matrix. The effects of the block copolymer to epoxy monomer ratios, the block copolymer length and the processing methods on the structure, property and kinetics of formation have been investigated by SAXS, DSC, rheology and DMA. These results provide new insights into how to design processes to promote the ordering of nanoparticles in bulk materials. |
Friday, March 9, 2018 9:12AM - 9:24AM |
X43.00007: Nanoplate Alignment and Self-Assembly in Diblock Copolymer Nanocomposites Nadia Krook, Manuel Maréchal, Patrice Rannou, Christopher Murray, Russell Composto Polymer nanocomposites (PNCs) are formed by incorporating nanoparticles (NPs) into polymeric matrices. PNC characteristics depend not only on the material of each component, but also on the distribution, organization, and, for anisotropic NPs, the orientation of the inclusions. However, limited work has been completed to achieve precise alignment of anisotropic NPs in PNCs via self-assembly methods. This work investigates lamellar-forming poly(styrene-b-methyl methacrylate) (PS-b-PMMA, Mn= 38k-b-36.8k g/mol) with domains parallel to the substrate as a platform to align polyethylene glycol (PEG, Mn = 5 kg/mol) grafted ytterbium and erbium doped gadolinium trifluoride rhombic nanoplates (GdF3:Yb/Er). The plates’ longest and shortest diagonals and thicknesses measure 35 nm, 22 nm, and 3 nm, respectively. The thin-film nanocomposites, prepared by spin-coating and thermal annealing, were characterized with electron microscopy. The GdF3:Yb/Er not only segregate to the PMMA domain, but also align in the lamellae up 20 wt%. Beyond 20 wt%, the block copolymer is disordered and the nanoplates are randomly oriented. These results extend our understanding of PNC phase behavior, enabling us to create new, self-assembling materials with the potential for anisotropic throughput properties. |
Friday, March 9, 2018 9:24AM - 9:36AM |
X43.00008: Computer Simulation of Block Copolymer Nanocomposites Javier Diaz, Marco Pinna, Andrei Zvelindovsky, Ignacio Pagonabarraga Block Copolymers are macromolecules composed of blocks of different repeated units. In the simplest case, diblock copolymers can self-assembly into ordered structures, and its morphology and overall properties can be modified by the presence of nanoparticles. The resulting nanocomposite can be highly ordered, and the its properties depend on both the pure polymeric matrix and the shape, chemistry and volume fraction of the colloids. |
Friday, March 9, 2018 9:36AM - 9:48AM |
X43.00009: Preparation and Characterization of Silver Nanoparticle Incorporated Polydimethylsiloxane for Implanted Medical Devices Falon Kalutantirige, Buddhika Gayani, Ayomi Dilhari, Manjula Weerasekera, Nilwala Kottegoda, Dilru Ratnaweera
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Friday, March 9, 2018 9:48AM - 10:00AM |
X43.00010: The Effect of Composition on the Morphology of Hybrid Inorganic-Organic Diblock Copolymer Electrolytes Gurmukh Sethi, Irune Villaluenga, Nitash Balsara Block copolymer electrolytes are advantageous for applications in lithium batteries due to chemical stability and tunable nanostructures. Inorganic-organic diblock copolymer electrolytes couple the ionic conductivity and mechanical strength desired in polymer electrolytes and exhibit microphase separation due to internal repulsive interactions, leading to unique phase transitions. The phase behavior of poly(ethylene oxide) (PEO)-block-polyhedral oligomeric silsesquioxane (POSS) acrylate, synthesized using nitroxide-mediated radical polymerization (NMP), with lithium bis(trifluoromethane)sulfonimide (LiTFSI) salt is systematically studied by varying the diblock composition and salt concentration. Using small angle X-ray scattering (SAXS) at different temperatures the morphology and the Flory-Huggins interaction parameter is obtained to quantify the thermodynamic interactions within the system. Due to the high degree of conformational asymmetry and strong repulsive interactions between the two polymer blocks, the morphological study reveals phase transitions that are not traditionally observed in diblock copolymers. |
Friday, March 9, 2018 10:00AM - 10:12AM |
X43.00011: Intercolloidal Potentials of Mean Force mediated by Homo- and Diblock Polymer Solutions Elucidated by Field-Theoretic Simulations Nick Sherck, Kris Delaney, M. Scott Shell, Glenn Fredrickson Our work probes how polymers of arbitrary design and chemistry in solution mediate the intercolloidal potential of mean force (PMF). Investigations are conducted using Field-Theoretic simulations, which subsequently yield intercolloidal PMF inputs for coarse-grained, particle based simulations. To realize the potential of polymers in colloidal stabilization and/or colloidal assembly, theory and computation are used synergistically to explore the polymer design space (e.g. molecular weight, volume fraction, architecture, interactions and charges). Here, we develop a general approach using complex Langevin sampling of field-theoretic polymer models between colloidal surfaces to provide exact solutions for colloidal-mediated PMFs for polymers of arbitrary design – explicitly including the effects of fluctuations. We show results for several model homopolymer and diblock polymer cases, illustrating the effects of fluctuations and comparing the explicit simulation results to various simple theoretical models. |
Friday, March 9, 2018 10:12AM - 10:24AM |
X43.00012: Effect of Copolymer Sequence on Mechanical Properties of Simulated Polymer Nanoparticle Composites Alex Trazkovich, Lisa Hall We simulate a simple nanocomposite consisting of a single spherical nanoparticle surrounded by coarse-grained polymer chains. The polymers are composed of two different monomer types, with different interaction strengths with the nanoparticle. We examine the effect of copolymer sequence and monomer-nanoparticle interaction strength on structure (using the monomer-nanoparticle radial distribution function), relaxation times (using the end-to-end and bond vector autocorrelation functions), and dynamic moduli (using the stress autocorrelation function). We measure these properties as a function of distance from the nanoparticle surface and find significant effects of copolymer sequence on the range and magnitude of the interphase of slowed dynamics and increased modulus surrounding the nanoparticle. Our work is motivated by design questions surrounding tire tread compounds, composed primarily of styrene-butadiene rubber copolymer (with potentially controllable block structure) and reinforced with carbon black and/or silica nanoparticles, though here we focus on the basic physical trends present in greatly simplified and uncrosslinked systems. |
Friday, March 9, 2018 10:24AM - 10:36AM |
X43.00013: Probe-SAXS and Deformation Studies on Nano-composite gels with 2D-Pair Distribution Function Analysis Kengo Nishi, Mitsuhiro Shibayama The information about the spatial distribution of fillers during stretching is essential to investigate a reinforcement effect of the mechanical properties of nanocomposite materials. Small angle scattering during stretching is a powerful tool for this purpose though 2D anisotropic scattering patterns are difficult to interpret. In this study, we propose how to evaluate 2D pair distribution function (2D PDF), which is the statistical information of spatial distribution in real space, from 2D anisotropic scattering patterns. From 2D PDFs, we obtained detailed and concrete structural information about the elongated PDAM-NP gel, such as affine and non-affine displacements of directly attached and homogeneously dispersed silica nanoparticles, respectively. These results strongly indicate that our 2D PDF analysis will provide deep insight into internal structure of polymer nanocomposites hidden in the anisotropic scattering patterns. |
Friday, March 9, 2018 10:36AM - 10:48AM |
X43.00014: Effect on Thermal and Mechanical Properties of Polystyrene Chain Grafting on Silica Nanoparticles Nazam Sakib, Yung Pyo Koh, Sindee Simon Thermal and rheological analysis of a silica - grafted polystyrene nanocomposite sample is carried out using the differential scanning calorimerty (DSC) and the rheometry. Measured properties are compared to those of a neat polymer of similar molecular weight. At 20% silica loading, the glass transition temperature of the nanocomposite is increased by 1.2 K and the step change in heat capacity (ΔCp) at the Tg for the nanocomposite is found to be reduced by 9%, indicating reduced segmental mobility of the grafted polymer chains. Absolute Cp measurements similarly show a decrease in both the glassy and liquid heat capacity values, with a decrease of 11% in absolute Cp observed at Tg. The viscoelastic response of the nanocomposite also changes significantly upon nanoparticle addition. The plateau modulus (GN0) is found to be increased by at least 30% as compared to the neat polymer sample and a shift of the terminal flow regime to lower frequencies is observed. Experiments in the glassy regime are in progress. |
Friday, March 9, 2018 10:48AM - 11:00AM |
X43.00015: The Effect of Dispersing Solvent Quality on the Microstructures and Properties of Polymer Nanocomposites Sol Mi Oh, Mozhdeh Abbasi, Kay Saalwaechter, So Youn Kim When nanoparticles are incorporated into the polymer matrix in polymer nanocomposites (PNCs), a good dispersion is required to achieve the desired physical properties. The size of particle/polymers, surface chemistry of particles, and grafting/adsorption polymer density on nanoparticles can affect the polymer-nanoparticle interactions at the interfaces and thus can change the state of dispersions. However, relatively less attention is paid to the role of the solvent for initial dispersion. |
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