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.

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

The effects of the chain structure and the intramolecular interaction energy of an A/B copolymer on the miscibility of the binary blends of the copolymer and homopolymer C have been studied by means of a Monte Carlo simulation. In the system, the interactions between segments A, B and C are more repulsive than those between themselves. In order to study the effect of the chain structure of the A/B copolymer on the miscibility, the alternating, random and block copolymers were introduced in the simulations, respectively. The simulation results show that the miscibility of the binary blends strongly depends on the intramolecular interaction energy ((ε) over bar (AB)) between segments A and B within the A/B copolymers. The higher the repulsive interaction energy, the more miscible the A/B copolymer and homopolymer C are. For the diblock copolymer/homopolymer blends, they tend to form micro phase domains. However, the phase domains become so small that the blend can be considered as a homogeneous phase for the alternating copolymer/ homopolymer blends. Furthermore, the investigation of the average end-to-end distance ((h) over bar) in different systems indicates that the copolymer chains tend to coil with the decrease Of (ε) over bar (AB) whereas the (h) over bar of the homopolymer chains depends on the chain structure of the copolymers.

Phase behavior of polymer blends

The present report deals with some results on phase behavior, miscibility and phase separation for several polymer blends casting from solutions. These blends are grouped as the amorphous polymer blends, blends containing a crystalline polymer or two crystalline polymers. The blends of PMMA/PVAc were miscible and underwent phase separation at elevated temperature, exhibited LCST behavior. The benzoylated PPO has both UCST and LCST nature. For the systems composed of crystalline polymer poly(ethylene oxide) and amorphous polyurethane, of two crystalline polymers poly(epsilon-caprolactone) and poly[3,3,-bis-(chloromethyl) oxetane], appear a single T-g, indicating these blends are miscible. The interaction parameter B's were determined to be -14 J cm(-3), -15 J cm(-3) respectively. Phase separation of phenolphthalein poly(ether ether sulfone)/PEO blends were discussed in terms of thermal properties, such as their melting and crystallization behavior.

Monte Carlo simulation of phase behavior of polymer blends with special interactions

Full Paper: The phase, behavior of A-B-random copolymer/C-homopolymer, blends with special interaction was studied by a. Monte, Carlo simulation in two dimensions. The interaction between I segment A and segment C was repulsive, whereas it was attractive between segment B and segment C. The simulation results showed that the blend became two large co-continuous phase domains at lower segment-B component compositions, indicating that the blend showed spinodal decomposition. With an increase of the segment-B component, the miscibility between the copolymer,and the polymer was gradually improved up to being miscible. In addition, it was found that segment B tended to move to the surface of the copolymer phase in the case of a lower component of segment B. On the other hand, if was observed that the average, end-to-end distances ((h) over bar) for both copolymer and polymer changed slowly with increasing segment-B component of the copolymer up to 40%, thereafter they increased considerably with increasing segment B component. Moreover, it was found that the (h) over bar of the copolymer was obviously shorter than that of the homopolymer for the segment-B composition, region from 0% to 80%. Finally, a, phase diagram showing I phase and - II phase regions under the condition of constant-temperature is presented.

Reactive reinforcement of the interface of high performance polymer blends by PMR-POI

The effect of PMR-polyimide(POI) as the interfacial agent on the interface characteristics, morphology features and crystallization of poly (ether sulfone) /poly (phenylene sulfide) (PES/PPS) and poly(ether ether ketone)/poly (ether sulfone) (PEEK/PES) partly miscible blends were investigated by means of the scanning electron microscopy, WAXD and XPS surface analysis. It is found that the interfacial adhesion was enhanced remarkably, the size of the dispersed phase particles was reduced significantly and the miscibility was improved by the addition of POI. During melt blending cross-link and/or grafting reaction of POI with PES, PEEK and PPS homopolymers was detected, however the reaction activity of POI with PPS was much higher than that of PES and PEEK. It was also found that POI was an effective nucleation agent of the crystallization of PPS.

Studies on polymer blends with special reference to NBR/PVC and CR/PVC blends

The study is undertaken on PVC blends because of their all-round importance-One of the most prominent needs of PVC in application end-use is permanent plasticizationlo. Butadiene-acrylonitrile rubber (NBR) has been utilized as permanent plasticizer for PVC since the 1940s for wire and cable insulation, food contact, and pondliners used for oil containment23'24. Also plasticized PVC has been added to vulcanizable nitrile rubber, to yield improved ozone, thermal ageing, and chemical resistance resulting in applications including fuel hose covers, gaskets, conveyor belt covers, and printing roll covers. This blend is miscible in the range of 23 to 45 per cent acrylonitrile content in the butadiene-acrylqnitrile copolymerzs. The first phase of the study was directed towards modification blends. These blends, in addition to the polymers, require a host of additives like curatives for the NBR phase and stabilizers for the PVC phase26of the existing PVC blends, especially NBR/PVC. The second phase of the study was directed towards the development of novel PVC based blends. Chloroprene rubber (polychloroprene) (CR) is structurally similar to PVC and hence is likely to form successful blends with PVC32.

Thermal properties of nylon6/ABS polymer blends: Compatibilizer effect

Nylon6/ABS binary blends are incompatible and need to be compatibilized to achieve better performance under impact tests. Poly(methyl methacrylate/maleic anhydride) (MMA-MA) is used in this work to compatibilize in situ nylon6/ABS immiscible blends. The MA functional groups, from MMA-MA copolymers, react with NH2 groups giving as products nylon molecules grafted to MMA-MA molecules. Those molecular species locate in the nylon6/ABS blend interfacial region increasing the local adhesion. MMA-MA segments are completely miscible with the SAN rich phase from the ABS. The aim of this work is to study the effects of ABS and compatibilizing agent on the melting and crystallization of nylon6/ABS blends. This effect has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). Incorporation of this compatibilizer and ABS showed little effect on the melting behavior of the PA6 crystalline phase, in general. DMTA analysis confirmed the system immiscibility and showed evidence of compatibility between the two phases, nylon6 and ABS, produced by MMA-MA copolymer presence. The nylon6/ABS blend morphology, observed by transmission electron microscopy (TEM), changes significantly by the addition of the MMA-MA compatibilizer. A better dispersion of ABS in the nylon6 phase is observed. © 2004 Kluwer Academic Publishers.

Ultra-flexible nonvolatile memory based on donor-acceptor diketopyrrolopyrrole polymer blends

Flexible memory cell array based on high mobility donor-acceptor diketopyrrolopyrrole polymer has been demonstrated. The memory cell exhibits low read voltage, high cell-to-cell uniformity and good mechanical flexibility, and has reliable retention and endurance memory performance. The electrical properties of the memory devices are systematically investigated and modeled. Our results suggest that the polymer blends provide an important step towards high-density flexible nonvolatile memory devices.

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.

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.