Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Corona Degradation of the Polymer Insulator Samples under Different Fog Conditions

Corona discharges resulting from the metal parts of insulators and the line hardware affect the long term performance of the polymeric insulators used for outdoor application and can lead to its eventual failure. The authors previous work, involved in developing a new methodology to evaluate the performance of polymeric shed materials subjected to corona stresses in the presence of natural fog condition, results revealed more surface hydroxylation thereby resulting in more loss of hydropobhicity. With the increase in industrialization, there is an increase in acidic component of the rain as well as the fog (moisture). The present work, reports the effect of acid fog on the corona performance of the polymeric insulators for both AC and DC excitation, interesting results are obtained. A comparison of the experimental investigations revealed that the acidic fog has more effect than that of the normal fog. This fact has been confirmed by physico-chemical analysis like the scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS) and contact angle measurement. The effect of DC corona is found to be lesser in comparison with the AC; however the hydroxylation induced by the DC corona under the presence of fog is similar with that of AC excitation.

Engineering a multi-biofunctional composite using poly(ethylenimine) decorated graphene oxide for bone tissue regeneration

Toward preparing strong multi-biofunctional materials, poly(ethylenimine) (PEI) conjugated graphene oxide (GO_PEI) was synthesized using poly(acrylic acid) (PAA) as a spacer and incorporated in poly( e-caprolactone) (PCL) at different fractions. GO_PEI significantly promoted the proliferation and formation of focal adhesions in human mesenchymal stem cells (hMSCs) on PCL. GO_PEI was highly potent in inducing stem cell osteogenesis leading to near doubling of alkaline phosphatase expression and mineralization over neat PCL with 5% filler content and was approximate to 50% better than GO. Remarkably, 5% GO_ PEI was as potent as soluble osteoinductive factors. Increased adsorption of osteogenic factors due to the amine and oxygen containing functional groups on GO_ PEI augment stem cell differentiation. GO_ PEI was also highly efficient in imparting bactericidal activity with 85% reduction in counts of E. coli colonies compared to neat PCL at 5% filler content and was more than twice as efficient as GO. This may be attributed to the synergistic effect of the sharp edges of the particles along with the presence of the different chemical moieties. Thus, GO_ PEI based polymer composites can be utilized to prepare bioactive resorbable biomaterials as an alternative to using labile biomolecules for fabricating orthopedic devices for fracture fixation and tissue engineering.

3D scaffold alters cellular response to graphene in a polymer composite for orthopedic applications

Graphene-based polymer nanocomposites are being studied for biomedical applications. Polymer nanocomposites can be processed differently to generate planar two-dimensional (2D) substrates and porous three-dimensional (3D) scaffolds. The objective of this work was to investigate potential differences in biological response to graphene in polymer composites in the form of 2D substrates and 3D scaffolds. Polycaprolactone (PCL) nanocomposites were prepared by incorporating 1% of graphene oxide (GO) and reduced graphene oxide (RGO). GO increased modulus and strength of PCL by 44 and 22% respectively, whereas RGO increased modulus and strength by 22 and 16%, respectively. RGO increased the water contact angle of PCL from 81 degrees to 87 degrees whereas GO decreased it to 77 degrees. In 2D, osteoblast proliferated 15% more on GO composites than on PCL whereas RGO composite showed 17% decrease in cell proliferation, which may be attributed to differences in water wettability. In 3D, initial cell proliferation was markedly retarded in both GO (36% lower) and RGO (55% lower) composites owing to increased roughness due to the presence of the protruding nanoparticles. Cells organized into aggregates in 3D in contrast to spread and randomly distributed cells on 2D discs due to the macro-porous architecture of the scaffolds. Increased cell-cell contact and altered cellular morphology led to significantly higher mineralization in 3D. This study demonstrates that the cellular response to nanoparticles in composites can change markedly by varying the processing route and has implications for designing orthopedic implants such as resorbable fracture fixation devices and tissue scaffolds using such nanocomposites. (c) 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 732-749, 2016.

The damage evaluation of rigid particle filled polymer

In this paper, the rigid particle filled polymer is studied in the hope to understand the real damage mechanisms. Two damage parameters were introduced and measured. One is the macro-damage of the materials calculated from the modulus measured, another is micro-damage describing the interfacial debonding or the percentage of the particle debonded from the matrix. The damage rate of the macro damage decreases, while the micro damage increases with the applied stress.

Deformation and Failure of Polymer Bonded Explosives under Diametric Compression Test

The tensile deformation and failure of polymer bonded explosives (PBXs), a particulate composite, is studied in this paper. Two HMX-based PBXs with different binder were selected for study. A diametric compression test, in which a disc-shaped specimen is loaded diametrically, was chosen to generate tensile failure in the materials. The quasi-static tensile properties and the tensile creep properties were studied by using conventional displacement transducers to measure the lateral strain along the horizontal diameter. The whole-field in-plane creep deformation was measured by using the technique of high resolution moire´ interferometry. Real time microscopic examination was conducted to monitor the process of deformation and failure of PBXs by using a scanning electron microscope equipped with a loading stage. A manifold method (MM) was used to simulate the deformation and failure of PBX samples under the diametric compression test, including the crack initiation, crack propagation and final cleavage fracture. The mechanisms of deformation and failure of PBXs under diametric compression were analyzed. The diametric compression test and the techniques developed in this research have proven to be applicable to the study of tensile properties of PBXs.

Dispersion rheology of carbon nanotubes in a polymer matrix

We report on rheological properties of a dispersion of multiwalled carbon nanotubes in a viscous polymer matrix. Particular attention is paid to the process of nanotubes mixing and dispersion, which we monitor by the rheological signature of the composite. The response of the composite as a function of the dispersion mixing time and conditions indicates that a critical mixing time t* needs to be exceeded to achieve satisfactory dispersion of aggregates, this time being a function of nanotube concentration and the mixing shear stress. At shorter times of shear mixing t< t*, we find a number of nonequilibrium features characteristic of colloidal glass and jamming of clusters. A thoroughly dispersed nanocomposite, at t> t*, has several universal rheological features; at nanotube concentration above a characteristic value nc ∼2-3 wt. % the effective elastic gel network is formed, while the low-concentration composite remains a viscous liquid. We use this rheological approach to determine the effects of aging and reaggregation. © 2006 The American Physical Society.

Polymers with aligned carbon nanotubes: Active composite materials

We review the current state of the polymer-carbon nanotube composites field. The article first covers key points in dispersion and stabilization of nanotubes in a polymer matrix, with particular attention paid to ultrasonic cavitation and shear mixing. We then focus on the emerging trends in nanocomposite actuators, in particular, photo-stimulated mechanical response. The magnitude and even the direction of this actuation critically depend on the degree of tube alignment in the matrix; in this context, we discuss the affine model predicting the upper bound of orientational order of nanotubes, induced by an imposed strain. We review how photo-actuation in nanocomposites depend on nanotube concentration, alignment and entanglement, and examine possible mechanisms that could lead to this effect. Finally, we discuss properties of pure carbon nanotube networks, in form of mats or fibers. These systems have no polymer matrix, yet demonstrate pronounced viscoelasticity and also the same photomechanical actuation as seen in polymer-based composites. © 2008 Elsevier Ltd. All rights reserved.

Tailoring the electrical properties of carbon nanotube-polymer composites

Advances in functionality and reliability of nanocomposite materials require careful formulation of processing methods to ultimately realize the desired properties. An extensive study of how the variation in fabrication process would affect the mechanism of conductivity and thus the final electrical properties of the carbon nanotube-polymer composite is presented. Some of the most widely implemented procedures are addressed, such as ultrasonication, melt shear mixing, and addition of surfactants. It is hoped that this study could provide a systematic guide to selecting and designing the downstream processing of carbon nanocomposites. Finally, this guide is used to demonstrate the fabrication and performance of a stretchable (pliable) conductor that can reversibly undergo uniaxial strain of over 100%, and other key applications are discussed. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure, deformation and failure of polymer bonded explosives

Polymer bonded explosives (PBXs) are highly particle filled composite materials comprised of explosive crystals and a polymeric binder (ca. 5-10% by weight). The microstructure and mechanical properties of two pressed PBXs with different binder systems were studied in this paper. The initial microstructure of the pressed PBXs and its evolution under different mechanical aggressions were studied, including quasi-static tension and compression, ultrasonic wave stressing and long-pulse low-velocity impact. Real-time microscopic observation of the PBXs under tension was conducted by using a scanning electron microscope equipped with a loading stage. The mechanical properties under tensile creep, quasi-static tension and compression were studied. The Brazilian test, or diametrical compression, was used to study the tensile properties. The influences of pressing pressures and temperatures, and strain rates on the mechanical properties of PBXs were analyzed. The mesoscale damage modes in initial pressed samples and the samples insulted by different mechanical aggressions, and the corresponding failure mechanisms of the PBXs under different loading conditions were analyzed.