Highly compressible behavior of polymer mediated three-dimensional network of graphene foam

The compressive behavior of graphene foam (GF) and its polymer (polydimethyl siloxane) (PDMS) infiltrated structure are presented. While GF showed an irreversible compressibility, the GF/PDMS structure revealed a highly reversible mechanical behavior up to many cycles of compression and also possesses a six times higher compressive strength. In addition, the strain rate demonstrated a negligible effect on both the maximum achieved stress and energy absorption in the GF/PDMS structure. The mechanical responses of both GF and GF/PDMS structure are compared with carbon nanotubes based cellular structure and its composite with PDMS, where GF/PDMS presented a dominant mechanical characteristic among other carbon based micro foam structures. Therefore, the improved mechanical properties of GF/PDMS suggest its potential for dampers, cushions, packaging, etc.

The key role of polymer grafted nanoparticles in the phase miscibility of an LCST mixture

Blends of bromo-terminated polystyrene (PS-Br) and poly(vinyl methylether) (PVME) exhibit lower critical solution temperatures. In this study, PS-Br was designed by atom transfer radical polymerization and was converted to thiol-capped polystyrene (PS-SH) by reacting with thiourea. The silver nanoparticles (nAg) were then decorated with covalently bound PS-SH macromolecules to improve the phase miscibility in the PS-Br-PVME blends. Thermally induced demixing in this model blend was followed in the presence of polystyrene immobilized silver nanoparticles (PS-g-nAg). The graft density of the PS macromolecules was estimated to be ca. 0.78 chains per nm(2). Although the matrix and the grafted molecular weights were similar, PS-g-nAg particles were expelled from the PS phase and were localized in the PVME phase of the blends. This was addressed with respect to intermediate graft density and favourable PS-PVME contacts from microscopic interactions point of view. Interestingly, blends with 0.5 wt% PS-g-nAg delayed the spinodal decomposition temperature in the blends by ca. 18 degrees C with respect to the control blends. The scale of cooperativity, as determined by differential scanning calorimetry, increased only marginally in the case of PS-g-nAg; however, it increased significantly in the presence of bare nAg particles.

Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide: outstanding mechanical properties

A unique strategy was adopted here to improve the compatibility between the components of an immiscible polymer blend and strengthen the interface. PMMA, a mutually miscible polymer to both PVDF and ABS, improved the compatibility between the phases by localizing at the blends interface. This was supported by the core-shell formation with PMMA as the shell and ABS as the core as observed from the SEM micrographs. This phenomenon was strongly contingent on the concentration of PMMA in the blends. This strategy was further extended to localize graphene oxide (GO) sheets at the blends interface by chemically coupling it to PMMA (PMMA-g-GO). A dramatic increment of ca. 84% in the Young's modulus and ca. 124% in the yield strength was observed in the presence of PMMA-g-GO with respect to the neat blends. A simultaneous increment in both the strength and the modulus was observed in the presence of PMMA-g-GO whereas, only addition of GO resulted in a moderate improvement in the yield strength. This study reveals that a mutually miscible polymer can render compatibility between the immiscible pair and can improve the stress transfer at the interface.

Dispersion of polymer grafted nanoparticles in polymer nanocomposite films: Insights from surface x-ray scattering and microscopy

Dispersion of nanoparticles in polymer nanocomposite films determines the application potential of these systems as novel materials with unique physical properties. Grafting polymers to, mostly inorganic, nanoparticles has been suggested as an effective strategy to enhance dispersion and hence the efficacy of materials. In this review, we discuss the various parameters which control dispersion of polymer grafted nanoparticles in polymer nanocomposite films. We discuss how surface x-ray scattering and microscopy can provide complementary and unique information in thin polymer nanocomposite films to unravel the subtle interplay of entropic and surface interactions, mediated by confinement, that leads to enhanced dispersion of the nanoparticles in these films. (C) 2014 AIP Publishing LLC.

Heterogeneity in Dye-TiO2 Interactions Dictate Charge Transfer Efficiencies for Diketopyrrolopyrrole-Based Polymer Sensitized Solar Cells

Power conversion efficiency of a solar cell is a complex parameter which usually hides the molecular details of the charge generation process. For rationally tailoring the overall device efficiency of the dye-sensitized solar cell, detailed molecular understanding of photoinduced reactions at the dye-TiO2 interface has to be achieved. Recently, near-IR absorbing diketopyrrolopyrrole-based (DPP) low bandgap polymeric dyes with enhanced photostabilities have been used for TiO2 sensitization with moderate efficiencies. To improve the reported device performances, a critical analysis of the polymerTiO(2) interaction and electron transfer dynamics is imperative. Employing a combination of time-resolved optical measurements complemented by low temperature EPR and steady-state Raman spectroscopy on polymerTiO(2) conjugates, we provide direct evidence for photoinduced electron injection from the TDPP-BBT polymer singlet state into TiO2 through the C-O group of the DPP-core. A detailed excited state description of the electron transfer process in films reveals instrument response function (IRF) limited (<110 fs) charge injection from a minor polymer fraction followed by a picosecond recombination. The major fraction of photoexcited polymers, however, does not show injection indicating pronounced ground state heterogeneity induced due to nonspecific polymerTiO(2) interactions. Our work therefore underscores the importance of gathering molecular-level insight into the competitive pathways of ultrafast charge generation along with probing the chemical heterogeneity at the nanoscale within the polymerTiO2 films for optimizing photovoltaic device efficiencies.

Functionality preservation with enhanced mechanical integrity in the nanocomposites of the metal-organic framework, ZIF-8, with BN nanosheets

Metal-organic frameworks (MOFs) and boron nitride both possess novel properties, the former associated with microporosity and the latter with good mechanical properties. We have synthesized composites of the imidazolate based MOF, ZIF-8, and few-layer BN in order to see whether we can incorporate the properties of both these materials in the composites. The composites so prepared between BN nanosheets and ZIF-8 have compositions ZIF-1BN, ZIF-2BN, ZIF-3BN and similar to ZIF-4BN. The composites have been characterized by PXRD, TGA, XPS, electron microscopy, IR, Raman and solid state NMR spectroscopy. The composites possess good surface areas, the actual value decreasing only slightly with the increase in the BN content. The CO2 uptake remains nearly the same in the composites as in the parent ZIF-8. More importantly, the addition of BN markedly improves the mechanical properties of ZIF-8, a feature that is much desired in MOFs. Observation of microporous features along with improved mechanical properties in a MOF is indeed noteworthy. Such manipulation of properties can be profitably exploited in practical applications.

Visible light assisted photocatalytic degradation of organic dyes on TiO2-CNT nanocomposites

Carbon nanotubes (CNTs) uniformly decorated with nano-anatase TiO2 particles corresponding to different TiO2-CNT weight ratios (up to 90 % TiO2:10 % CNT) were prepared by employing sol-gel process. The nanocomposites were characterized by X-ray diffraction, IR, Raman, Scanning electron microscopy, Transmission electron microscopy, Photoluminescence, BET surface area and diffuse reflectance measurements. The composites show visible light assisted photocatalytic property, for example, the 90 % TiO2-10 % CNT composite completely degrades Indigo Carmine dye within 1 h of exposure to visible light. Similarly, Orange G and Congo Red dyes were decomposed within 2 h under visible light irradiation. The excellent visible light photocatalytic property of the composite is attributed to the synergetic effect of photoexcitation and photosensitization. This is due to the special nanoarchitecture wherein TiO2 nanoparticles are anchored to CNT surface that provides high specific interfacial area for photon absorption and electron trapping. Visible light assisted degradation profile of Indigo Carmine in the presence of TiO2-CNT nanocomposite and TEM image of the TiO2-CNT nanocomposite.

Optically transparent polymer devices for in situ assessment of cell electroporation

In order to study cell electroporation in situ, polymer devices have been fabricated from poly-dimethyl siloxane with transparent indium tin oxide parallel plate electrodes in horizontal geometry. This geometry with cells located on a single focal plane at the interface of the bottom electrode allows a longer observation time in both transmitted bright-field and reflected fluorescence microscopy modes. Using propidium iodide (PI) as a marker dye, the number of electroporated cells in a typical culture volume of 10-100 mu l was quantified in situ as a function of applied voltage from 10 to 90 V in a series of 2-ms pulses across 0.5-mm electrode spacing. The electric field at the interface and device current was calculated using a model that takes into account bulk screening of the transient pulse. The voltage dependence of the number of electroporated cells could be explained using a stochastic model for the electroporation kinetics, and the free energy for pore formation was found to be kT at room temperature. With this device, the optimum electroporation conditions can be quickly determined by monitoring the uptake of PI marker dye in situ under the application of millisecond voltage pulses. The electroporation efficiency was also quantified using an ex situ fluorescence-assisted cell sorter, and the morphology of cultured cells was evaluated after the pulsing experiment. Importantly, the efficacy of the developed device was tested independently using two cell lines (C2C12 mouse myoblast cells and yeast cells) as well as in three different electroporation buffers (phosphate buffer saline, electroporation buffer and 10 % glycerol).

Effects of refractive index mismatch in optical CT imaging of polymer gel dosimeters

Purpose: Proposing an image reconstruction technique, algebraic reconstruction technique-refraction correction (ART-rc). The proposed method takes care of refractive index mismatches present in gel dosimeter scanner at the boundary, and also corrects for the interior ray refraction. Polymer gel dosimeters with high dose regions have higher refractive index and optical density compared to the background medium, these changes in refractive index at high dose results in interior ray bending. Methods: The inclusion of the effects of refraction is an important step in reconstruction of optical density in gel dosimeters. The proposed ray tracing algorithm models the interior multiple refraction at the inhomogeneities. Jacob's ray tracing algorithm has been modified to calculate the pathlengths of the ray that traverses through the higher dose regions. The algorithm computes the length of the ray in each pixel along its path and is used as the weight matrix. Algebraic reconstruction technique and pixel based reconstruction algorithms are used for solving the reconstruction problem. The proposed method is tested with numerical phantoms for various noise levels. The experimental dosimetric results are also presented. Results: The results show that the proposed scheme ART-rc is able to reconstruct optical density inside the dosimeter better than the results obtained using filtered backprojection and conventional algebraic reconstruction approaches. The quantitative improvement using ART-rc is evaluated using gamma-index. The refraction errors due to regions of different refractive indices are discussed. The effects of modeling of interior refraction in the dose region are presented. Conclusions: The errors propagated due to multiple refraction effects have been modeled and the improvements in reconstruction using proposed model is presented. The refractive index of the dosimeter has a mismatch with the surrounding medium (for dry air or water scanning). The algorithm reconstructs the dose profiles by estimating refractive indices of multiple inhomogeneities having different refractive indices and optical densities embedded in the dosimeter. This is achieved by tracking the path of the ray that traverses through the dosimeter. Extensive simulation studies have been carried out and results are found to be matching that of experimental results. (C) 2015 American Association of Physicists in Medicine.

Narrow band gap conjugated polymer for improving the photovoltaic performance of P3HT:PCBM ternary blend bulk heterojunction solar cells

A new D-A structured conjugated polymer (PBDO-T-TDP) based on electron-rich benzo 1,2-b:4,5-b'] difuran (BDO) containing conjugated alkylthiophene side chains with an electron-deficient diketopyrrolopyrrole (DPP) derivative is designed and synthesized. The polymer shows a narrow band gap with broad UV-Visible absorption spectra, which is in contrast to that of the P3HT:PCBM binary blend. Furthermore, its energy levels can meet the energetic requirement of the cascaded energy levels of P3HT and PCBM. Therefore, PBDO-T-TDP is used as a sensitizer in P3HT: PCBM based BHJ solar cells and its effect on their photovoltaic properties was investigated by blending them together at various weight ratios. It is observed that the resulting ternary blend system exhibited a significant improvement in the device performance (similar to 3.10%) as compared with their binary ones (similar to 2.15%). Such an enhancement in the ternary blend system is ascribed to their balanced hole and electron mobility along with uniform distribution of PBDO-T-TDP in the blend system, as revealed by organic field effect transistors and AFM studies.

Kinetics of dispersion of nanoparticles in thin polymer films at high temperature

We report the first detailed study of the kinetics of dispersion of nanoparticles in thin polymer films using temperature dependent in situ X-ray scattering measurements. We show a comparably enhanced dispersion at higher temperatures for systems which are otherwise phase segregated at room temperature. Detailed analysis of the time dependent X-ray reflectivity and diffuse scattering data allows us to explore the out-of-plane and in-plane mobility of the nanoparticles in the polymer films. While the out-of-plane motion is diffusive with a diffusion coefficient almost two orders of magnitude lower than that expected in bulk polymer, the in-plane one is found to be super-diffusive resulting in significantly larger in-plane displacement at similar time scales. We discuss the origin of the observed highly anisotropic motion of nanoparticles due to their slaved motion with respect to the anisotropic chain orientation and consequent diffusivity anisotropy of matrix chains. We also suggest strategies to utilize these observations to kinetically improve dispersion in otherwise thermodynamically segregated polymer nanocomposite films.

Chemical Functionalization of Graphene To Augment Stem Cell Osteogenesis and Inhibit Biofilm Formation on Polymer Composites for Orthopedic Applications

Toward designing the next generation of resorbable biomaterials for orthopedic applications, we studied poly(epsilon-caprolactone) (PCL) composites containing graphene. The role, if any, of the functionalization of graphene on mechanical properties, stem cell response, and biofilm formation was systematically evaluated. PCL composites of graphene oxide (GO), reduced GO (RGO), and amine-functionalized GO (AGO) were prepared at different filler contents (1%, 3%, and 5%). Although the addition of the nanoparticles to PCL markedly increased the storage modulus, this increase was largest for GO followed by AGO and RGO. In vitro cell studies revealed that the AGO and GO particles significantly increased human mesenchymal stem cell proliferation. AGO was most effective in augmenting stem cell osteogenesis leading to mineralization. Bacterial studies revealed that interaction with functionalized GO induced bacterial cell death because of membrane damage, which was further accentuated by amine groups in AGO. As a result, AGO composites were best at inhibiting biofilm formation. The synergistic effect of oxygen containing functional groups and amine groups on AGO imparts the optimal combination of improved modulus, favorable stem cell response, and biofilm inhibition in AGO-reinforced composites desired for orthopedic applications. This work elucidates the importance of chemical functionalization of graphene in polymer composites for biomedical applications.

Enzymatically degradable EMI shielding materials derived from PCL based nanocomposites

In this study, two different types of multiwall carbon nanotubes (MWNTs) namely pristine (p-MWNTs) and amine functionalized (a-MWNTs) were melt-mixed with polycaprolactone (PCL) to develop biodegradable electromagnetic interference (EMI) shielding materials. The bulk electrical conductivity of the nanocomposites was assessed using broadband dielectric spectroscopy and the structural properties were evaluated using dynamic mechanical thermal analysis (DMTA). Both the electrical conductivity and the structural properties improved after the addition of MWNTs and were observed to be proportional to the increasing fractions in the nanocomposites. The shielding effectiveness of the nanocomposites was studied using a vector network analyzer (VNA) in a broad range of frequencies, X-band (8 to 12 GHz) and K-u-band (12 to 18 GHz) on toroidal samples. The shielding effectiveness significantly improved on addition of MWNTs, more in the case of p-MWNTs than in a-MWNTs. For instance, at a given fraction of MWNTs (3 wt%), PCL with p-MWNTs and a-MWNTs showed a shielding effectiveness of -32 dB and -29 dB, respectively. Moreover, it was observed that reflection was the primary mechanism of shielding at lower fractions of MWNTs, while absorption dominated at higher fractions in the composites. As one of the rationales of this work was to develop biodegradable EMI shielding materials to address the challenges concerning electronic waste, the effect of different MWNTs on the biodegradability of PCL composites was assessed through enzymatic degradation. The enzymatic degradation of the samples cut from the hot pressed films by bacterial lipase was investigated. It was noted that a-MWNTs exhibited almost similar degradation rate as the control PCL sample; however, p-MWNTs showed a slower degradation rate. This study demonstrates the potential use of PCL-MWNT composites as flexible, light weight and eco-friendly EMI shielding materials.

Low-Wear High-Friction Behavior of Copper Matrix Composites Dispersed With an In Situ Polymer Derived Ceramic

We show that copper-matrix composites that contain 20 vol. % of an in situ processed, polymer-derived, ceramic phase constituted from Si-C-N have unusual friction-and-wear properties. They show negligible wear despite a coefficient of friction (COF) that approaches 0.7. This behavior is ascribed to the lamellar structure of the composite such that the interlamellar regions are infused with nanoscale dispersion of ceramic particles. There is significant hardening of the composite just adjacent to the wear surface by severe plastic deformation.