Unique nanoporous antibacterial membranes derived through crystallization induced phase separation in PVDF/PMMA blends

In this study, a unique method was adopted to design porous membranes through crystallization induced phase separation in PVDF/PMMA (poly(vinylidene fluoride)/poly(methyl methacrylate)) blends. By etching out PMMA, which segregates either in the interlamellar and/or in the interspherulitic regions of the blends, nanoporous hierarchical structures can be derived. Different nanoparticles like titanium dioxide (TiO2), silver nanoparticle (Ag) decorated carbon nanotubes (Ag-CNTs), TiO2 decorated CNTs (TiO2-CNTs), Ag decorated TiO2 (Ag-TiO2) and Ag-TiO2 decorated CNTs (Ag@TiO2-CNTs) were synthesized and melt mixed with 80/20 PVDF/PMMA blends to render antibacterial activity to the membranes. Scanning electron microscopy (SEM) was used to study the crystalline morphology of the membranes. A significant improvement in the trans-membrane flux was obtained in the blends with Ag@TiO2 decorated CNTs as compared to the membranes derived from the neat blends, which can be attributed to the interconnected pores in these membranes. Both qualitative and quantitative studies of antifouling and antibacterial activity (using E. coli as a model bacterium) were performed using the standard plate count method. SEM micrographs clearly showed that the antifouling activity of the membranes was improved with addition of Ag@TiO2-CNTs. In the quantitative standard plate count method, the bacterial colony significantly decreased with the addition of Ag@TiO2-CNTs as against neat blends. This study opens a new avenue in the fabrication of polymer blend based membranes for water filtration.

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).

Porous membranes designed from bi-phasic polymeric blends containing silver decorated reduced graphene oxide synthesized via a facile one-pot approach

In this work, porous membranes were designed by selectively etching the PEO phase, by water, from a melt-mixed PE/PEO blend. The pure water flux and the resistance across the membrane were systematically evaluated by employing an indigenously developed cross flow membrane setup. Both the phase morphology and the cross sectional morphology of the membranes was assessed by scanning electron microscopy and an attempt was made to correlate the observed morphology with the membrane performance. In order to design antibacterial membranes for water purification, partially reduced graphene oxide (rGO), silver nanoparticles (Ag) and silver nanoparticles decorated with rGO (rGO-Ag) were synthesized and incorporated directly into the blends during melt mixing. The loss of viability of bacterial cells was determined by the colony counting method using E. coli as a model bacterium. SEM images display that the direct contact with the rGO-Ag nanoparticles disrupts the cell membrane. In addition, the rGO-Ag nanoparticles exhibited a synergistic effect with respect to bacterial cell viability in comparison to both rGO and Ag nanoparticles. The possible mechanism associated with the antibacterial activity in the membranes was discussed. This study opens new avenues in designing antibacterial membranes for water purification.

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.

Peculiar morphological transitions induced by nanoparticles in polymeric blends: retarded relaxation or altered interfacial tension?

Nanoparticles of different shapes can induce peculiar morphologies in binary polymer blends depending on their position. It is envisaged that the increased yield stress of the filled phase slows down the relaxation resulting in arresting the peculiar morphologies which otherwise is thermodynamically unfavourable due to the increased interfacial area. This essentially means that the highly irregular structures can be preserved even without altering the interfacial tension between the phases! On the other hand, in the case of interfacially adsorbed particles, the resulting solid-like interface can also preserve the irregular structures. These phenomenal transitions in filled blends are very different from the classical copolymer compatibilized polymer blends. Moreover, these irregular structures can further pave way in designing conducting polymer blends involving conducting nanoparticles and revisiting our understanding of the concept of double percolation!

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.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.

Microwave absorbers designed from PVDF/SAN blends containing multiwall carbon nanotubes anchored cobalt ferrite via a pyrene derivative

Lightweight and flexible electromagnetic shielding materials were designed by selectively localizing multiwall carbon nanotubes (MWNTs) anchored magnetic nanoparticles in melt mixed co-continuous blends of polyvinylidene fluoride (PVDF) and poly(styrene-co-acrylonitrile) (SAN). In order to facilitate better dispersion, the MWNTs were modified using pyrenebutyric acid (PBA) via pi-pi stacking. While one of the two-targeted properties, i.e., high electrical conductivity, was achieved by PBA modified MWNTs, high magnetic loss was accomplished by introducing nickel (NF) or cobalt ferrites (CF). Moreover, the attenuation by absorption can be tuned either by using NF (58% absorption) or CF (64% absorption) in combination with PBA-MWNTs. More interestingly, when CF was anchored on to MWNTs via the pyrene derivative, the minimum reflection loss attained was -55 dB in the Ku band (12-18 GHz) frequency and with a large bandwidth. In addition, the EM waves were blocked mostly by absorption (70%). This study opens new avenues in designing flexible and lightweight microwave absorbers.

Thermally flexible epoxy/cellulose blends mediated by an ionic liquid

Blends between the widely used thermoset resin, epoxy, and the most abundant organic material, natural cellulose are demonstrated for the first time. The blending modification induced by charge transfer complexes using a room temperature ionic liquid, leads to the formation of thermally flexible thermoset materials. The blend materials containing low concentrations of cellulose were optically transparent which indicates the miscibility at these compositions. We observed the existence of intermolecular hydrogen bonding between epoxy and cellulose in the presence of the ionic liquid, leading to partial miscibility between these two polymers. The addition of cellulose improves the tensile mechanical properties of epoxy. This study reveals the use of ionic liquids as a compatible processing medium to prepare epoxy thermosets modified with natural polymers.

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.

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.

Attenuating microwave radiation by absorption through controlled nanoparticle localization in PC/PVDF blends

Nanoscale ordering in a polymer blend structure is indispensable to obtain materials with tailored properties. It was established here that controlling the arrangement of nanoparticles, with different characteristics, in co-continuous PC/PVDF (polycarbonate/poly(vinylidene fluoride)) blends can result in outstanding microwave absorption (ca. 90%). An excellent reflection loss (RL) of ca. -71 dB was obtained for a model blend structure wherein the conducting (multiwall carbon nanotubes, MWNTs) and the magnetic inclusions (Fe3O4) are localized in PVDF and the dielectric inclusion (barium titanate, BT) is in PC. The MWNTs were modified using polyaniline, which facilitates better charge transport in the blends. Furthermore, by introducing surface active groups on BT nanoparticles and changing the macroscopic processing conditions, the localization of BT nanoparticles can be tailored, otherwise BT nanoparticles would localize in the preferred phase (PVDF). In this study, we have shown that by ordered arrangement of nanoparticles, the incoming EM radiation can be attenuated. For instance, when PANI-MWNTs were localized in PVDF, the shielding was mainly through reflection. Now by localizing the conducting inclusion and the magnetic lossy materials in PVDF and the dielectric materials in PC, an outstanding shielding effectiveness of ca. -37 dB was achieved where shielding was mainly through absorption (ca. 90%). Thus, this study clearly demonstrates that lightweight microwave absorbers can be designed using polymer blends as a tool.

Nanoparticle induced miscibility in LCST polymer blends: critically assessing the enthalpic and entropic effects

The use of copolymer and polymer blends widened the possibility of creating materials with multilayered architectures. Hierarchical polymer systems with a wide array of micro and nanostructures are generated by thermally induced phase separation (TIPS) in partially miscible polymer blends. Various parameters like the interaction between the polymers, concentration, solvent/non-solvent ratio, and quenching temperature have to be optimized to obtain these micro/nanophase structures. Alternatively, the addition of nanoparticles is another strategy to design materials with desired hetero-phase structures. The dynamics of the polymer nanocomposite depends on the statistical ordering of polymers around the nanoparticle, which is dependent on the shape of the nanoparticle. The entropic loss due to deformation of polymer chains, like the repulsive interactions due to coiling and the attractive interactions in the case of swelling has been highlighted in this perspective article. The dissipative particle dynamics has been discussed and is correlated with the molecular dynamics simulation in the case of polymer blends. The Cahn Hillard Cook model on variedly shaped immobile fillers has shown difference in the propagation of the composition wave. The nanoparticle shape has a contributing effect on the polymer particle interaction, which can change the miscibility window in the case of these phase separating polymer blends. Quantitative information on the effect of spherical particles on the demixing temperature is well established and further modified to explain the percolation of rod shaped particles in the polymer blends. These models correlate well with the experimental observations in context to the dynamics induced by the nanoparticle in the demixing behavior of the polymer blend. The miscibility of the LCST polymer blend depends on the enthalpic factors like the specific interaction between the components, and the solubility product and the entropic losses occurring due to the formation of any favorable interactions. Hence, it is essential to assess the entropic and enthalpic interactions induced by the nanoparticles independently. The addition of nanoparticles creates heterogeneity in the polymer phase it is localized. This can be observed as an alteration in the relaxation behavior of the polymer. This changes the demixing behavior and the interaction parameter between the polymers. The compositional changes induced due to the incorporation of nanoparticles are also attributed as a reason for the altered demixing temperature. The particle shape anisotropy causes a direction dependent depletion, which changes the phase behavior of the blend. The polymer-grafted nanoparticles with varying grafting density show tremendous variation in the miscibility of the blend. The stretching of the polymer chains grafted on the nanoparticles causes an entropy penalty in the polymer blend. A comparative study on the different shaped particles is not available up to date for understanding these aspects. Hence, we have juxtaposed the various computational studies on nanoparticle dynamics, the shape effect of NPs on homopolymers and also the cases of various polymer blends without nanoparticles to sketch a complete picture on the effect of various particles on the miscibility of LCST blends.

Designer porous antibacterial membranes derived from thermally induced phase separation of PS/PVME blends decorated with an electrospun nanofiber scaffold

We report the development of porous membranes by thermally induced phase separation of a PS/PVME (polystyrene/polyvinylmethyl ether]) blend, which is a typical LCST mixture. The morphology of the membrane after etching out the PVME phase was characterized by scanning electron microscopy. To give the membrane an antibacterial surface, polystyrene (PS) and polyvinyl(methyl ether)]-alt-maleic anhydride (PVME-MAH) with silver nanoparticles (nAg) were electrospun on the membrane surface. Pure water flux was evaluated by using a cross-flow membrane setup. The microgrooved fibers changed the flux across the membrane depending on the surface properties. The antibacterial properties of the membrane were confirmed by the reduction in the colony count of E. coli. The SEM images show the disruption of the bacterial cell membrane and the antibacterial mechanism was discussed.

A strategy to achieve enhanced electromagnetic interference shielding at ultra-low concentration of multiwall carbon nanotubes in P alpha MSAN/PMMA blends in the presence of a random copolymer PS-r-PMMA

A unique strategy was adopted to achieve an ultra-low electrical percolation threshold of multiwall carbon nanotubes (MWNTs) (0.25 wt%) in a classical partially miscible blend of poly-alpha-methylstyrene-co-acrylonitrile and poly(methyl methacrylate) (P alpha MSAN/PMMA), with a lower critical solution temperature. The polymer blend nanocomposite was prepared by standard melt-mixing followed by annealing above the phase separation temperature. In a two-step mixing protocol, MWNTs were initially melt-mixed with a random PS-r-PMMA copolymer and subsequently diluted with 85/15 P alpha MSAN/PMMA blends in the next mixing step. Mediated by the PS-r-PMMA, the MWNTs were mostly localized at the interface and bridged the PMMA droplets. This strategy led to enhanced electromagnetic interference (EMI) shielding effectiveness at 0.25 wt% MWNTs through multiple scattering from MWNT-covered droplets, as compared to the blends without the copolymer, which were transparent to electromagnetic radiation.