Tailoring the dispersion of multiwall carbon nanotubes in co-continuous PVDF/ABS blends to design materials with enhanced electromagnetic interference shielding

Highly conducting composites were derived by selectively localizing multiwall carbon nanotubes (MWNTs) in co-continuous PVDF/ABS (50/50, wt/wt) blends. The electrical percolation threshold was obtained between 0.5 and 1 wt% MWNTs as manifested by a dramatic increase in the electrical conductivity by about six orders of magnitude with respect to the neat blends. In order to further enhance the electrical conductivity of the blends, the MWNTs were modified with amine terminated ionic liquid (IL), which, besides enhancing the interfacial interaction with PVDF, facilitated the formation of a network like structure of MWNTs. This high electrical conductivity of the blends, at a relatively low fraction (1 wt%), was further explored to design materials that can attenuate electromagnetic (EM) radiation. More specifically, to attenuate the EM radiation by absorption, a ferroelectric phase was introduced. To accomplish this, barium titanate (BT) nanoparticles chemically stitched onto graphene oxide (GO) sheets were synthesized and mixed along with MWNTs in the blends. Intriguingly, the total EM shielding effectiveness (SE) was enhanced by ca. 10 dB with respect to the blends with only MWNTs. In addition, the effect of introducing a ferromagnetic phase (Fe3O4) along with IL modified MWNTs was also investigated. This study opens new avenues in designing materials that can attenuate EM radiation by selecting either a ferroelectric (BT-GO) or a ferromagnetic phase (Fe3O4) along with intrinsically conducting nanoparticles (MWNTs).

A Surlyn/magnesium oxide nanocomposite as an effective water vapor barrier for organic device encapsulation

A reactive polymer nanocomposite system was proposed as an effective water vapor barrier material for organic device encapsulation. Nanosized magnesium oxide (MgO) was synthesized by the solution combustion technique using two different fuels, lactose and alanine. The purity and crystallite size of MgO were determined from X-ray diffraction studies. The surface areas and porosity measurements were used to determine the water adsorption capacities of MgO. Nanocomposites with various concentrations (wt% = 0.25, 0.5, 1 and 2.5) of MgO were prepared using Surlyn as the base polymer. The permeation rate of moisture through the fabricated films was calculated using calcium degradation test and these rates were further used to calculate the diffusivities. Accelerated aging experiments were conducted to study the performance of organic photovoltaic devices encapsulated with synthesized films under accelerated weathering conditions. The performance of the barrier materials with synthesized MgO was also compared to that obtained with commercial MgO. The films containing MgO obtained from lactose exhibited better barrier properties compared to other films made with commercial MgO and MgO synthesized using alanine as well as other nanocomposites reported in the literature.

Polyvinylidene fluoride based lightweight and corrosion resistant electromagnetic shielding materials

Various NixCo1-x alloys (with x varying from 0-60 wt%, Ni: nickel, Co: cobalt) were prepared by vacuum arc melting and mixed with polyvinylidene fluoride (PVDF) to design lightweight, flexible and corrosion resistant materials that can attenuate electromagnetic radiation. The saturation magnetization scaled with the fraction of Co in the alloy. Two key properties such as high-magnetic permeability and high-electrical conductivity were targeted. While the former was achieved using a Ni-Co alloy, multiwalled carbon nanotubes (CNTs) in the composites accomplished the latter. A unique approach was adopted to prepare the composites wherein PVDF powder along with CNTs and Ni-Co flakes were made into a paste, using a solvent, followed by hot pressing. Interestingly, CNTs facilitated in uniform dispersion of the Ni-Co alloy in PVDF, as manifested from synergistic improvement in the electrical conductivity. A significant improvement in the shielding effectiveness (41 dB, >99.99% attenuation) was achieved with the addition of 50 wt% of Ni40Co60 alloy and 3 wt% CNTs. Intriguingly, due to the unique processing technique adopted here, the flexibility of the composites was retained and more interestingly, the composites were resistant to corrosion as compared to only Ni-Co alloy.

Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

Role of stacking fault energy on texture evolution revisited

Three materials, pure aluminium, Al-4 wt.% Mg, alpha-brass have been chosen to understand the evolution of texture and microstructure during rolling. Pure Al develops a strong copper-type rolling texture and the deformation is entirely slip dominated. In Al-4Mg alloy, texture is copper-type throughout the deformation. The advent of Cu-type shear bands in the later stages of deformation has a negligible effect on the final texture. alpha-brass shows a characteristic brass-type texture from the early stages of rolling. Extensive twinning in the intermediate stages of deformation (epsilon(t) similar to 0.5) causes significant texture reorientation towards alpha-fiber. Beyond 40% reduction, deformation is dominated by Bs-type shear bands, and the banding coincides with the evolution of <111>parallel to ND components. The crystallites within the bands preferentially show <110>parallel to ND components. The absence of the Cu component throughout the deformation process indicates that, for the evolution of brass-type texture, the presence of Cu component is not a necessary condition. The final rolling texture is a synergistic effect of deformation twinning and shear banding.

Simultaneous enhancement in mechanical strength, electrical conductivity, and electromagnetic shielding properties in PVDF-ABS blends containing PMMA wrapped multiwall carbon nanotubes

A unique approach was adopted to drive the multiwall carbon nanotubes (MWNTs) to the interface of immiscible PVDF-ABS blends by wrapping the nanotubes with a mutually miscible homopolymer (PMMA). A tailor made interface with an improved stress transfer was achieved in the blends with PMMA wrapped MWNTs. This manifested in an impressive 108% increment in the tensile strength and 48% increment in the Young's modulus with 3 wt% PMMA wrapped MWNTs in striking contrast to the neat blends. As the PMMA wrapped MWNTs localized at the interface of PVDF-ABS blends, the electrical conductivity could be tuned with respect to only MWNTs, which were selectively localized in the PVDF phase, driven by thermodynamics. The electromagnetic shielding properties were assessed using a vector network analyser in a broad range of frequency, X-band (8-12 GHz) and Ku-band (12-18 GHz). Interestingly, enhanced EM shielding was achieved by this unique approach. The blends with only MWNTs shielded the EM waves mostly by reflection however, the blends with PMMA wrapped MWNTs (3 wt%) shielded mostly by absorption (62%). This study opens new avenues in designing materials, which show simultaneous improvement in mechanical, electrical conductivity and EM shielding properties.

Engineering nanostructured polymer blends with controlled nanoparticle location for excellent microwave absorption: a compartmentalized approach

In order to obtain better materials, control over the precise location of nanoparticles is indispensable. It is shown here that ordered arrangements of nanoparticles, possessing different characteristics (electrical/ magnetic dipoles), in the blend structure can result in excellent microwave absorption. This is manifested from a high reflection loss of ca. -67 dB for the best blend structure designed here. To attenuate electromagnetic radiation, the key parameters of high electrical conductivity and large dielectric/magnetic loss are targeted here by including a conductive material multiwall carbon nanotubes, MWNTs], ferroelectric nanostructured material with associated relaxations in the GHz frequency barium titanate, BT] and lossy ferromagnetic nanoparticles nickel ferrite, NF]. In this study, bi-continuous structures were designed using 50/50 (by wt) blends of polycarbonate (PC) and polyvinylidene fluoride (PVDF). The MWNTs were modified using an electron acceptor molecule, a derivative of perylenediimide, which facilitates p-p stacking with the nanotubes and stimulates efficient charge transport in the blends. The nanoscopic materials have specific affinity towards the PVDF phase. Hence, by introducing surface-active groups, an ordered arrangement can be tailored. To accomplish this, both BT and NF were first hydroxylated followed by the introduction of amine-terminal groups on the surface. The latter facilitated nucleophilic substitution reactions with PC and resulted in their precise location. In this study, we have shown for the first time that by a compartmentalized approach, superior EM attenuation can be achieved. For instance, when the nanoparticles were localized exclusively in the PVDF phase or in both the phases, the minimum reflection losses were ca. -18 dB (for the MWNT/BT mixture) and -29 dB (for the MWNT/NF mixture), and the shielding occurred primarily through reflection. Interestingly, by adopting the compartmentalized approach wherein the lossy materials were in the PC phase and the conductive materials (MWNT) were in the PVDF phase, outstanding reflection losses of ca. -57 dB (for the BT and MWNT combination) and -67 dB (for the NF and MWNT combination) were noted and the shielding occurred primarily through absorption. Thus, the approach demonstrates that nanoscopic structuring in the blends can be achieved under macroscopic processing conditions and this strategy can further be explored to design microwave absorbers.

Contrasting Effects of Graphene Oxide and Poly(ethylenimine) on the Polymorphism in Poly(vinylidene fluoride)

The nature of interaction between a heteronucleating agent (graphene oxide, GO) and a strongly polar macromolecule (poly(ethylenimine), PEI) with poly(vinylidene fluoride) (PVDF) influencing the crystalline structure and morphology has been systematically investigated in this work. PEI interacts with PVDF via ion-dipole interaction, which helps in lowering the free energy barrier for nucleation thereby promoting faster crystallization. In contrast, besides interacting with PVDF, GO also promotes heteronucleation in PVDF. We observed that both GO and PEI have very different effects on the overall crystalline morphology of PVDF. For instance, the neat PVDF showed a mixture of both alpha and beta phases when cooled from the melt. However, incorporation of 0.1 wt % GO resulted in phase transformation from the stable alpha-phase to polar beta-polymorph in PVDF. In contrast, PEI, which also resulted in faster crystallization in PVDF predominantly, resulted in the stable alpha- phase. Various techniques like Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry were employed to confirm the phase transformations in PVDF. PEI was further grafted onto GO nanosheets to understand the combined effects of both GO and PEI on the polymorphism in PVDF. The PVDF/PEI-GO composite showed a mixture of phases, predominantly rich in a. These phenomenal effects were further analyzed and corroborated with the specific interaction between GO and PEI with PVDF using X-ray photon scattering (XPS) and NMR. In addition, the dielectric permittivity increased significantly in the presence of GO and PEI in the composites. For instance, PVDF/PEI-GO showed the highest permittivity of 39 at 100 Hz.

Bioengineering of AAV2 Capsid at Specific Serine, Threonine, or Lysine Residues Improves Its Transduction Efficiency in Vitro and in Vivo

We hypothesized that the AAV2 vector is targeted for destruction in the cytoplasm by the host cellular kinase/ubiquitination/proteasomal machinery and that modification of their targets on AAV2 capsid may improve its transduction efficiency. In vitro analysis with pharmacological inhibitors of cellular serine/threonine kinases (protein kinase A, protein kinase C, casein kinase II) showed an increase (20-90%) on AAV2-mediated gene expression. The three-dimensional structure of AAV2 capsid was then analyzed to predict the sites of ubiquitination and phosphorylation. Three phosphodegrons, which are the phosphorylation sites recognized as degradation signals by ubiquitin ligases, were identified. Mutation targets comprising eight serine (S) or seven threonine (T) or nine lysine (K) residues were selected in and around phosphodegrons on the basis of their solvent accessibility, overlap with the receptor binding regions, overlap with interaction interfaces of capsid proteins, and their evolutionary conservation across AAV serotypes. AAV2-EGFP vectors with the wild-type (WT) capsid or mutant capsids (15 S/T -> alanine A] or 9 K -> arginine R] single mutant or 2 double K -> R mutants) were then evaluated in vitro. The transduction efficiencies of 11 S/T -> A and 7 K -> R vectors were significantly higher (similar to 63-90%) than the AAV2-WT vectors (similar to 30-40%). Further, hepatic gene transfer of these mutant vectors in vivo resulted in higher vector copy numbers (up to 4.9-fold) and transgene expression (up to 14-fold) than observed from the AAV2-WT vector. One of the mutant vectors, S489A, generated similar to 8-fold fewer antibodies that could be cross-neutralized by AAV2-WT. This study thus demonstrates the feasibility of the use of these novel AAV2 capsid mutant vectors in hepatic gene therapy.

Targeted Modifications in Adeno-Associated Virus Serotype 8 Capsid Improves Its Hepatic Gene Transfer Efficiency In Vivo

Recombinant adeno-associated virus vectors based on serotype 8 (AAV8) have shown significant promise for liver-directed gene therapy. However, to overcome the vector dose dependent immunotoxicity seen with AAV8 vectors, it is important to develop better AAV8 vectors that provide enhanced gene expression at significantly low vector doses. Since it is known that AAV vectors during intracellular trafficking are targeted for destruction in the cytoplasm by the host-cellular kinase/ubiquitination/proteasomal machinery, we modified specific serine/threonine kinase or ubiquitination targets on the AAV8 capsid to augment its transduction efficiency. Point mutations at specific serine (S)/threonine (T)/lysine (K) residues were introduced in the AAV8 capsid at the positions equivalent to that of the effective AAV2 mutants, generated successfully earlier. Extensive structure analysis was carried out subsequently to evaluate the structural equivalence between the two serotypes. scAAV8 vectors with the wild-type (WT) and each one of the S/T -> Alanine (A) or K-Arginine (R) mutant capsids were evaluated for their liver transduction efficiency in C57BL/6 mice in vivo. Two of the AAV8-S -> A mutants (S279A and S671A), and a K137R mutant vector, demonstrated significantly higher enhanced green fluorescent protein (EGFP) transcript levels (similar to 9- to 46-fold) in the liver compared to animals that received WT-AAV8 vectors alone. The best performing AAV8 mutant (K137R) vector also had significantly reduced ubiquitination of the viral capsid, reduced activation of markers of innate immune response, and a concomitant two-fold reduction in the levels of neutralizing antibody formation in comparison to WT-AAV8 vectors. Vector bio-distribution studies revealed that the K137R mutant had a significantly higher and preferential transduction of the liver (106 vs. 7.7 vector copies/mouse diploid genome) when compared to WT-AAV8 vectors. To further study the utility of the K137R-AAV8 mutant in therapeutic gene transfer, we delivered human coagulation factor IX (h. FIX) under the control of liver-specific promoters (LP1 or hAAT) into C57BL/6 mice. The circulating levels of h. FIX: Ag were higher in all the K137R-AAV8 treated groups up to 8 weeks post-hepatic gene transfer. These studies demonstrate the feasibility of the use of this novel AAV8 vectors for potential gene therapy of hemophilia B.

Design and morphology control of a thiophene derivative through electrospraying using various solvents

In the present work, electrospraying of an organic molecule is carried out using various solvents, obtaining fibril structures along with a range of distinct morphologies. Solvent characteristics play a major role in determining the morphology of the organic material. A thiophene derivative (7,9-di(thiophen-2-yl)-8H-cyclopentaa]acenaphthylen-8-one) (DTCPA) of donor-acceptor-donor (DAD) architecture is used to study this solvent effect. Seven solvents with decreasing vapour pressure are selected for experiments. Electrospraying is conducted at a solution concentration of 1.5 wt% and a constant applied voltage of 15 kV. Gradual transformation in morphology of the electrospun product from spiked-spheres to only spikes is observed. A mechanism describing this transformation is proposed based on electron micrograph analysis and XRD analysis. These data indicate that the morphological change is due to the synergistic effect of both vapour pressure and dielectric constant of the solvents. Through a reasonable control of the crystallite size and morphology along with the proposal of the transformation mechanism, this study elucidates electrospraying as a prospective method for designing architectures in organic electronics.

Selective localisation of multi walled carbon nanotubes in polypropylene/natural rubber blends to reduce the percolation threshold

Polypropylene and natural rubber blends with multiwalled carbon nanotube (PP/NR + MWCNT nanocomposites) were prepared by melt mixing. The melt rheological behaviour of neat PP and PP/NR blends filled with different loadings (1, 3, 5, 7 wt%) of MWCNT was studied. The effect of PP/NR blends (with compositions, 80/20,50/50, 20/80 by wt) on the rheological percolation threshold was investigated. It was found that blending PP with NR (80/20 and 50/50 composition) reduced the rheological percolation threshold from 5 wt% to 3 wt% MWCNT. The melt rheological behaviour of the MWCNT filled PP/NR blends was correlated with the morphology observations from high resolution transmission electron microscopic (HRTEM) images. In predicting the thermodynamically favoured location of MWCNT in PP/NR blend, the specific interaction of phospholipids in NR phase with MWCNTs was considered quantitatively. The MWCNTs were selectively localised in the NR phase. The percolation mechanism in MWCNT filled PP/NR blends was discussed and for each blend composition, the percolation mechanism was found to be different. (C) 2015 Elsevier Ltd. All rights reserved.

Novel architecture for anomalous strengthening of a particulate filled polymer matrix composite

We propose an architecture for dramatically enhancing the stress bearing and energy absorption capacities of a polymer based composite. Different weight fractions of iron oxide nano-particles (NPs) are mixed in a poly(dimethylesiloxane) (PDMS) matrix either uniformly or into several vertically aligned cylindrical pillars. These composites are compressed up to a strain of 60% at a strain rate of 0.01 s(-1) following which they are fully unloaded at the same rate. Load bearing and energy absorption capacities of the composite with uniform distribution of NPs increase by similar to 50% upon addition of 5 wt% of NPs; however, these properties monotonically decrease with further addition of NPs so much so that the load bearing capacity of the composite becomes 1/6th of PDMS upon addition of 20 wt% of NPs. On the contrary, stress at a strain of 60% and energy absorption capacity of the composites with pillar configuration monotonically increase with the weight fraction of NPs in the pillars wherein the load bearing capacity becomes 1.5 times of PDMS when the pillars consisted of 20 wt% of NPs. In situ mechanical testing of composites with pillars reveals outward bending of the pillars wherein the pillars and the PDMS in between two pillars, located along a radius, are significantly compressed. Reasoning based on effects of compressive hydrostatic stress and shape of fillers is developed to explain the observed anomalous strengthening of the composite with pillar architecture.

Engineering Nanostructures by Decorating Magnetic Nanoparticles onto Graphene Oxide Sheets to Shield Electromagnetic Radiations

In this study, a minimum, reflection loss of 70 a was achieved, for a 6 mm thick shield (at 17.1 GHz frequency) employing a unique approach. This was accomplished by engineering nanostructures through decoration of magnetic nanopartides (nickel, Ni) onto graphene oxide (GO) sheets. Enhanced electromagnetic (EM) shielding was derived by selectively, localizing the nanoscopic particles in a specific phase of polyethylene (PE)/poly(ethylene oxide) (PEO) blends. By introduction of a conducting inclusion (like multiwall carbon nanotubes, MWNTs) together with the engineered nanostructures (nickel-decorated GO, (GO-Ni), the shielding efficiency can be enhanced significantly in contrast to physically mixing the particles in the blends. For instance, the composites showed a shielding efficiency >25 dB for a combination of MWNTS (3 wt %) and Ni nanoparticles (52 wt %) in PE/PEO blends. However, similar shielding effectiveness could be achieved for a combination of MWNTs (3 wt %) and 10 vol % of GO-Ni where in the effective concentration of Ni was only 19 wt %. The GO-Ni sheets facilitated in an efficient charge transfer as manifested from high electrical conductivity in the blends besides enhancing the permeability in the blends. It is envisioned that GO is simultaneously reduced in the process of synthesizing GO-Ni, and this facilitated in efficient charge transfer between the neighboring CNTs. More interestingly, the blends With MWNTs/GO-Ni attenuated the incoming EM radiation mostly by absorption. This study opens new avenues in designing polyolefin-based lightweight shielding materials by engineering nanostructures for numerous applications.

Carbon-Nanohorn-Reinforced Polymer Matrix Composites: Synergetic Benefits in Mechanical Properties

Mechanical properties of single-walled carbon nanohoms (SWNH) and SWNH plus few-layer graphene (EG)-reinforced poly(vinyl alcohol) (PVA) matrix composites have been measured using the nanoindentation technique. The elastic modulus (E) and hardness (H) of PVA were found to improve by similar to 315% and similar to 135%, respectively, upon the addition of just 0.4 wt % SWNH. These properties were found to be comparable to those obtained upon the addition of 0.2 wt % single-walled nanotubes (SWNT) to PVA. Furthermore, upon binary addition of 0.2 wt % EG and 0.4 wt % SWNH to PVA, benefits in the form of similar to 400% and similar to 330% synergy in E and H, respectively, were observed, along with an increased resistance to viscoelastic deformation. The reasons for these improvements are discussed in terms of the dimensionality of nanocarbon, the effectiveness of nanocarbon and polymer matrix interaction, and the influence of nanocarbon on the degree of crystallinity of the polymer. The results from SWNH reinforcement in this study demonstrate the scope for a novel and, in contrast to SWNT composites, a commercially feasible opportunity for strengthening polymer matrices.