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.

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.

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!

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.

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly( ethylene oxide), poly(vinyl alcohol): and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water p-resent in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics.

Flow behavior of LDPE and its blends with LLDPE I and II: A comparative study

Studies on melt rheological properties of blends of low density polyethylene (LDPE) with selected grades of linear low density polyethylene (LLDPE), which differ widely in their melt flow indices, are reported, The data obtained in a capillary rheometer are presented to describe the effects of blend composition and shear rate on flow behavior index, melt viscosity, and melt elasticity. In general, blending of LLDPE I that has a low melt flow index (2 g/10 min) with LDPE results in a decrease of its melt viscosity, processing temperature, and the tendency of extrudate distortion, depending on blending ratio. A blending ratio around 20-30% LLDPE I seems optimum from the point of view of desirable improvement in processability behavior. On the other hand, blending of LLDPE II that has a high melt flow index (10 g/10 min) with LDPE offers a distinct advantage in increasing the pseudoplasticity of LDPE/LLDPE II blends.

Crystallization behaviour of polyethylene and i-polybutene-1 blends

The mutual influence of the components on the crystallization behaviour of polyblends, namely, isotactic polybutene-1 (PB) with low-density and high-density polyethylene (LDPE and HDPE), has been studied using techniques such as differential scanning calorimetry, infra-red spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy, etc. Each component in the blend is observed to crystallize independently. There is phase separation and incompatibility, as shown from tensile properties and scanning electron microscopic observation of the fracture surface of the blend. For HDPE-PE blends (<30% HDPE), unusual form I′ crystals of PB are observed along with the usual form II.

Studies on LDPE-cyanoethylated lignocellulosics blends using epoxy functionalized LDPE as compatibilizer

Rubberwood flour and cellulose have been plasticized by cyanoethylation and then blended with low-density polyethylene (LDPE). A small quantity of epoxy functionalized polyethylene i.e., polyethylene-co-glycidyl methacrylate (PEGMA) has been added to further enhance the mechanical properties. The mechanical properties were measured according to the standard ASTM methods. SEM analysis was performed for both fractured and unfractured blend specimens. The mechanical properties were improved by the addition of PEGMA compatibilizer. LDPE blends with cyanoethylated wood flour (CYWF) showed higher tensile strength and modulus than cyanoethylated cellulose CYC-LDPE blends. However CYC-LDPE blends exhibited higher relative elongation at break values as compared with the former. The TGA analysis showed lowering of thermal stability as the filler content is increased and degradation temperature of LDPE is shifted slightly to lower temperature. DSC analysis showed loss of crystallinity for the LDPE phase as the filler content is increased for both types of blends. Dielectric properties of the blends were similar to LDPE, but were lowered on adding PEGMA. (c) 2006 Wiley Periodicals, Inc.

Supermacroporous Polymer-Based Cryogel Bioreactor for Monoclonal Antibody Production in Continuous Culture Using Hybridoma Cells

Cryogel matrices composed of different polymeric blends were synthesized, yielding a unique combination of hydrophilicity and hydrophobicity with the presence or absence of charged surface. Four such cryogel matrices composed of polyacrylamide-chitosan (PAAC), poly(N-isopropylacrylamide)-chitosan, polyacrylonitrile (PAN), and poly(N-isopropylacrylamide) were tested for growth of different hybridoma cell lines and production of antibody in static culture. All the matrices were capable for the adherence of hybridoma cell lines 6A4D7, B7B10, and H9E10 to the polymeric surfaces as well as for the efficient monoclonal antibody (mAb) production. PAAC proved to be relatively better in terms of both mAb production and cell growth. Further, PAAC cryogel was designed into three different formats, monolith, disks, and beads, and used as packing material for packed-bed bioreactor. Longterm cultivation of 6A4D7 cell line on PAAC cryogel scaffold in all the three formats could be successfully done for a period of 6 weeks under static conditions. Continuous packed-bed bioreactor was setup using 6A4D7 hybridoma cell line in the three reactor formats. The reactors ran continuously for a period of 60 days during which mAb production and metabolism of cells in the bioreactors were monitored periodically. The monolith bioreactor performed most efficiently over a period of 60 days and produced a total of 57.5 mg of antibody in the first 30 days (in 500 mL) with a highest concentration of 115 mu g mL(-1), which is fourfold higher than t-flask culture. The results demonstrate that appropriate chemistry and geometry of the bioreactor matrix for cell growth and immobilization can enhance the reactor productivity. (C) 2010 American Institute of Chemical Engineers Biotechnol. Prog., 27: 170-180, 2011

Comparison of the miscibility strategies in poly(benzyl methacrylate)-polystyrene blends

Exothermic interactions like hydrogen bonding, ionic and charge transfer, etc., and ''copolymer effect'' are commonly used to induce miscibility in immiscible blends. The efficacy of these methods in promoting miscibility in poly(benzyl methacrylate) (PBMA)-polystyrene (PS) immiscible blends has been studied by suitably modifying the structure of the component polymers. It has been found that hydrogen bonding approach is most advantageous among these approaches as it involves the need for minimum interacting sites. It has also been shown that these results can be extended to the blends of poly(acrylate)s or poly(methacrylate)s with PS. (C) 1996 John Wiley & Sons, Inc.

On the formation of poly(ethyleneoxide)-poly(vinylalcohol) blends

Poly(ethyleneoxide)-poly(vinylalcohol) blends were prepared and characterized using thermal, spectroscopic and structural methods, By all indications the blends appear to be microscopically inhomogeneous with no strong interpolymer bonding. The high degree of crystallinity in PEO regions induces a significant degree of ordering in neighbouring PVA regions, as evident from thermal properties. PVA obtained from solvent evaporation exhibits an irreversible endothermic transition which could be order-disorder type. Both IR and NMR spectroscopies also suggest the presence of subtle structural ordering influence of PEO on PVA. It is found to be possible to prepare self supporting films of the blends which consists of fine dispersion of PEO and PVA in each other. (C) 1999 Elsevier Science Ltd. All rights reserved.

Solution grafting of maleic anhydride onto polyethylene and compatibilization of polyetylene-nylon blends

Maleic anhydride (MAH) has been grafted onto high density polyethylene (HDPE) with benzoyl peroxide (BOP) initiator in toluene solution. Maximum degree of grafting (12%) without crosslinking has been obtained using MAH/HDPE and BOP/HDPE weight ratios of 1.0 and 0.15 respectively, at 110 degrees C. The HDPE-g-MAH compatibilizer is found to drastically reduce the dispersed phase size and also to produce homogeneous blends for relatively low concentrations of dispersed phase in HDPE/nylon blends. Addition of this compatibilizer results in increase of tensile strength and modulus with increasing nylon content of HDPE/nylon blends, while the opposite is found for the blends without any added compatibilizer.

Spectral, thermal and electrical properties of poly(o- and m-toluidine) PVC blends prepared by solution blending

Poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) blends with polyvinylchloride (PVC) of five different compositions have been prepared by solution blending. The POT-PVC and PMT-PVC blends were prepared using THF as a solvent in which POT-HNO3, PMT-HNO3 bases and PVC are soluble. The blends have been characterized by spectral, thermal and electrical measurements. The results indicate the formation of blends at all the compositions presently studied. The thermal stability of the POT-PVC and PMT-PVC blends is higher than that of POT-HNO3 and PMT-HNO3 salts, respectively. Using the present method, POT/PMT can conveniently be blended with 30% wt/wt of PVC without significant loss in its conductivity. (C) 1998 Elsevier Science Ltd. All rights reserved.

Mechanical properties of Nylon-6/LDPE blends containing an epoxy resin compatibilizer

Binary and ternary blends of nylon-6/low density polyethylene (nylon-6/LDPE) and Nylon-6/LDPE/poly(ethylene-co-glycidyl methacrylate) were prepared by melt mixing. The blends exhibit two phase morphology with LDPE dispersed in the form of spherical domains in the nylon-6 matrix. The mechanical properties of the blends were measured by standard methods. It is shown that the use of the epoxy copolymer as a compatibilizer improves the impact strength of the blend as compared to nylon-6, which is attributed to better stress transfer across the interface due to the compatibilizer. The data for each mechanical property were also fitted into a best fit model equation and the method of steepest ascent was applied to arrive at the optimum composition of the blend for that property.