Novel strategy for ternary polymer blend compatibilization

A novel strategy for compatibilization of ternary polymer blends was described. PP (polyolefins)/PA6 (engineering plastics)/PS (styrene polymers) was selected as a model ternary blend system, and the compatibilization effect was investigated by means of SEM, rheometer, dynamic mechanical thermal analysis and mechanical testing. The results indicated that, as a ternary polymer blend compatibilizer, styrene and maleic anhydride dual monomers melt grafted polypropylene [PP-g-(MAH-co-St)] showed more effective compatibilization in the PP/PA6/PS ternary blend system than PP-g-MAH, PP-g-St and their mixture. The good compatibilizing effect of PP-g-(MAH-co-St) can be explained by two mechanisms. One is the in situ formation of [PP-g-(MAH-co-St)]-g-PA6 copolymer at the PP/PA6 interface, and the other is that it also contains styrene blocks, resulting in chemical affinity with PS and PP homopolymers.     

Nucleating agent induced impact fracture behavior change in PP/POE blend

This work was focused on the impact fracture behavior of polypropylene/ethylene-octene copolymer (PP/POE) blends with and without nucleating agent (NA). The crystallization morphologies of injection-molded-bar were analyzed by polarization optical microscope and the impact-fractured surface morphologies were characterized carefully through scanning electronic microscope. Our results show that the addition of 0.2 wt% α/or β-NA induces the great decrease of spherulites diameters companioned with the dramatically enhancement of PP/POE blend toughness. Virgin PP shows the typical brittle-fractured characteristic during the whole fracture process. PP/POE shows the less-ductile fracture feature with multiple-craze formation. The addition of NA into PP/POE blend changes the fractured surface feature from predominantly multiple-craze to predominantly shear yielding or shear yielding involving materials cavitations and second-crack re-initiation, respectively, indicating the change from brittle-like fracture mode to ductile fracture mode. The transformation of β → α during the impact process for β-NA nucleated samples has been observed; however, such transformation is suppressed by the presence of POE.     

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 SiO_x substrate at 145 °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. Prior to the investigation of dewetting, it is confirmed that this blend is miscible at 145 °C using grazing incidence ultra small-angle X-ray scattering (GIUSAX).     

Near-IR dye sensitization of polymer blend solar cells

We have fabricated ternary blend solar cells based on poly(3-hexylthiophene) (P3HT) as a donor material, poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (N2200) as an acceptor material, and a silicon naphthalocyanine derivative (SiNc) as a near-IR sensitizer. In order to discuss how molecular structures impact the dye sensitization in P3HT/N2200 solar cells, we studied two SiNc molecules with different axial groups: SiNc10 with decyldimethylsilyl oxide and SiNc6 with trihexylsilyl oxide. As a result, P3HT/N2200/SiNc10 ternary solar cells exhibited a power conversion efficiency of 1.4%, which is improved by 73% compared to P3HT/N2200 binary solar cells and also by 17% compared to P3HT/N2200/SiNc6 ternary solar cells. We discuss the origin of the improvement in the device performance in terms of dye location in ternary blend films.     

Low percolation threshold conductive device derived from a five-component polymer blend

In this work we report on the preparation of a solid, 3D, low percolation threshold conductive device prepared through the control of multiple encapsulation and multiple percolation effects in a 5 component polymer blend system through melt processing. Conductive polyaniline (PANI) is situated in the core of the 5 component continuous system comprised of high-density polyethylene (HDPE), polystyrene (PS), poly(methyl methacrylate)(PMMA) and poly(vinylidene fluoride)(PVDF). In this fashion, its percolation threshold can be reduced to below 5 vol%. The approach used here is thermodynamically controlled and is described by Harkins spreading theory. In this work the detailed morphology and continuity diagrams of binary, ternary, quaternary and finally quinary systems are progressively studied in order to systematically demonstrate the concentration regimes resulting in the formation of these novel multiple-encapsulated morphological structures. Initially, onion-type dispersed phase structures are prepared and it is shown that through the control of the composition of the inner and outer layers the morphology can be transformed to a hierarchical-self-assembled, multi-percolated structure. The influence of a copolymer on selected pairs in the encapsulated structure is also examined. The conductivity of the quinary blend system can be increased from 10⁻¹⁵ S cm⁻¹ (pure HDPE) to 10⁻⁵ S cm⁻¹ at 5 vol% PANI and up to 10⁻³ S cm⁻¹ for 10 vol% PANI. These are the highest conductivity values ever reported for these PANI concentrations in melt processed systems.     

Nanostructured polymer blend formed from poly(N-vinylpyrrolidone) and end-functional polystyrene

Phase structures of blends of poly(N-vinylpyrrolidone) (PVP) with SO₃H terminated polystyrene (PSS) were investigated. The PVP-PSS blends were macroscopically homogeneous, although the blends of PVP with polystyrene (PS) showed macroscopic phase separation. The PVP-PSS blends, however, showed two glass transitions indicating existence of two phases. Small-angle X-ray scattering measurements revealed the PVP-PSS blends formed mesomorphically ordered morphologies which change with variation of blend composition. The nano-organized phase separation in the PVP-PSS blends was caused due to hydrogen bonding of the PVP with the terminal SO₃H group of the PSS and repulsive interaction between PVP and main chain of the PSS.     

Phase separation in polymer blend thin films studied by differential AC chip calorimetry

AC chip calorimetry is used to study the phase separation behavior of 100 nm thin poly(vinyl methyl ether)/poly(styrene) (PVME/PS) blend films. Using the on-chip heaters, very short (10 ms-10 s) temperature jumps into the temperature window of phase separation are applied, simulating laser heating induced patterning. These temperature pulses produce a measurable shift in the glass transition temperature, evidencing phase separation. The effect of pulse length and height on phase separation can be studied. The thus phase separated PVME/PS thin films remix rapidly, in contrast with measurements in bulk. AC chip calorimetry seems to be a more sensitive technique than atomic force microscopy to detect the early stages of phase separation in polymer blend thin films.     

A novel type of shape memory polymer blend and the shape memory mechanism

A novel styrene-butadiene-styrene tri-block copolymer (SBS) and poly(?-caprolactone) (PCL) blend were introduced for its shape memory properties. Compared to the reported shape memory polymers (SMPs), this novel elastomer and switch polymer blend not only simplified the fabrication process but also offer a controllable approach for the study of mechanisms and the optimization of shape memory performances. Microstructures of this blend were characterized by differential scanning calorimetry (DSC), AFM microscope observation and tensile test. DSC results demonstrated the immiscibility between SBS and PCL. AFM images and stress-strain plot further confirmed the two-phase morphology within the blend. It was found that the SBS and PCL continuous phases contributed to the shape recovery and shape fixing performances, respectively. A detailed shape memory mechanism for this type of SMP system was then concluded and an optimized SMP system with both good recovery and fixing performances was designed from this mechanism.     

Transparent,conductive polymer blend coatings from latex-based dispersions

Flexible, transparent and conductive polymer blend coatings were prepared from aqueous dispersions of poly(3,4-ethylenedixoythiophene)/poly(styrenesulfonate) [PEDOT/PSS] gel particles (∼80 nm) and latex (∼300 nm). The stable dispersions were deposited as wet coatings onto poly(ethylene terephthalate) substrates and dried at 80 °C. Microstructure studies using tapping mode atomic force microscopy (TMAFM) indicate that a network-like microstructure formed during drying at 0.03 volume fraction PEDOT/PSS loading. In this network-like structure, the PEDOT/PSS phase was forced into the boundary regions between latex. In addition, migration of the PEDOT/PSS particles towards coating surface is likely during drying of the aqueous dispersions. The addition of a small amount of dimethyl sulfoxide (DMSO) in dispersions altered the distribution of the PEDOT/PSS phase. As PEDOT/PSS concentration increases to 0.15 volume fraction, the coating surface is dominated by the PEDOT/PSS phase. The effect of DMSO on microstructure becomes less apparent as PEDOT/PSS concentration increases. The conductivity of the polymer blend coatings increases in a percolation-like fashion with a threshold of ∼0.02 volume fraction PEDOT/PSS. The addition of DMSO in dispersions enhanced the coating conductivity beyond the threshold by more than two orders of magnitude. The highest conductivity, ∼3 S/cm, occurs at 0.20 volume fraction PEDOT/PSS concentration. The polymer blend coatings have good transparency with only a weak dependence of transparency on wavelength due to the small refractive index difference between filler and matrix.     

Temperature dependence of surface composition and morphology in polymer blend film

Thin films of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blend can phase separate upon heating to above its critical temperature. Temperature dependence of the surface composition and morphology in the blend thin film upon thermal treatment was studied using in situ X-ray photoelectron spectroscopy (XPS) and in situ atomic force microscopy (AFM). It was found that in addition to phase separation, the blend component preferentially diffused to and aggregated at the surface of the blend film, leading to the variation of surface composition with temperature. At 185 °C, above the critical temperature, the amounts of PMMA and SAN phases were comparable. At lower temperatures PMMA migrated to the surface, leading to a much higher PMMA surface content than in the bulk. The migration and preferential segregation of a blend component in thin films demonstrated here are responsible for the great difference between in situ and ex situ experimental (not real quenching or annealing) results of polymer blend films, and help explain the slow kinetics of surface phase separation at early stage for blend thin films reported in literature. This is significant for the control of surface properties of polymer materials.     

Effect of imidazole based polymer blend electrolytes for dye-sensitized solar cells in energy harvesting window glass applications

The exploration of polymer electrolyte in the field of dye sensitized solar cell (DSSC) can contribute to increase the invention of renewable energy applications. In the present work, the influence of imidazole on the poly (vinylidene fluoride) (PVDF)-poly (methyl methacrylate) (PMMA)-Ethylene carbonate (EC)-KI-I₂ polymer blend electrolytes has been evaluated. The different weight percentages of imidazole added into polymer blend electrolytes have been prepared by solution casting. The prepared films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), UV-visible spectra, photoluminescence spectra and impedance spectroscopy. The surface roughness texture of the film was analyzed by atomic force microscopy (AFM). The ionic conductivity of the optimized polymer blend electrolyte was determined by impedance measurement, which is 1.95×10^-3 S·cm^-1 at room temperature. The polymer electrolyte containing 40 wt% of imidazole content exhibits the highest photo-conversion efficiency of 3.04% under the illumination of 100 mW·cm^-2. Moreover, a considerable enhancement in the stability of the DSSC device was demonstrated.     

Effect of viscosity in ternary polymer blends displaying partial wetting phenomena

Partial wetting in a ternary polymer blend is the thermodynamic state where all three phases meet at a three-phase line of contact. Pickering emulsions, where solid particles situate at the interface of two other phases is a classic example of this state. This paper studies the presence of partial wetting in PE/PP/PS and in PE/PP/PC ternary polymer blends and examines, in particular, the influence of polyethylene viscosity on PS droplet formation at the PE/PP interface. Quantitative analysis of PS droplet growth and coverage at the PE/PP interface during static annealing were obtained by image analysis. A new approach was established to estimate the co-continuous PE/PP coarsening rate and was found to be in agreement with previous studies. In this work it is shown that the polyethylene viscosity can be of significant importance in ternary partial wetting when the interfacial driving force for partial wetting is weak and viscosity directly affects the quantity and size of PS droplets at the interface during annealing. The equilibrium between droplet stability at the interface, as predicted by spreading theory, and the interfacial mobility generated by coarsening determines the PS droplet size and surface coverage at the PE/PP interface.A ternary PE/PP/PC system, which displays a strong partial wetting driving force, was also investigated. The morphology of the blend system studied demonstrated a clear dominance of partial wetting over complete wetting.     

The loading-rate dependent fracture property of a toughened epoxy polymer

Summary The fracture energy of an elastomer-modified epoxy polymer was determined as a function of loading rate. Fracture tests were carried out by using compact tension specimens and standard Izod impact specimens. The fracture energy of the base epoxy was increased by the elastomeric additives. The extent of increase, however, was found to decrease with increasing loading rate.     

Observation of polymer interface instability

We observed with a confocal scanning laser microscope the interface between a liquid crystalline polymer (LCP) and polydimethylsiloxane (DMS) after they made contact. The initially flat interface became corrugated and the characteristic length of the corrugation increased gradually. The coarsening rate was found to be controlled by the viscosity (the molecular weight) of the DMS; as the viscosity was increased the rate became slower. The present interfacial instability may be related to the diffusion of the low molecular weight DMS into the LCP.     

Structural analysis of multicomponent nanoclay-containing polymer blends through simple model systems

A systematic approach was adopted to study multicomponent clay-containing nanocomposites using compatibilized and non-compatibilized blends of polyamide 6 (PA6)/acrylonitrile-butadiene-styrene terpolymer (ABS) and their organoclay (OMMT) nanocomposites. For this purpose PA6/styrene-acrylonitrile copolymer (SAN) based blends and nanocomposites were selected as simple model systems. In this way the role of each component of the systems, especially the clay, compatibilizer, and polybutadiene fraction on the formation of intercalated or exfoliated OMMT structures as well as resulting dynamic mechanical properties (DMA) could be elucidated. Structural analysis of the model systems using theoretical approach, and X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and DMA revealed that the most crucial factor in controlling the morphology and achieving different levels of dispersion is the extent of interaction between clay and the polymer matrix. Morphological analysis revealed that the OMMT layers were dispersed and exfoliated largely in the PA6 phase but, some were also accumulated at the rubber particle surface which remained non-intercalated. The effect of a compatibilizer on the dispersion of OMMT was not completely clear. The SAN based nanocomposites containing PA6 showed fully exfoliated OMMT structures, whereas the ABS based nanocomposites, having an additional rubber fraction, showed a mixed exfoliated and also partly non-intercalated morphology. The OMMT did not change the general occurrence of the co-continuous structures but refined the structures and led to mechanical stiffening as indicated by the DMA results. A correlation was established between the changes in the morphological states and the DMA properties.     

Role of block copolymer on the coarsening of morphology in polymer blend: Effect of micelles

The reactive compatibilization of polystyrene/ethylene‐α‐octene copolymer (PS/POE) blend via Friedel–Crafts alkylation reaction was investigated by rheology and electron microscope. It was found that the graft copolymer formed from interfacial reaction reduced the domain size and decreased the coarsening rate of morphology. The reduction of the interfacial tension is very limited according to the mean field theory even assuming that all block copolymer stays on the interface. With the help of self‐consistent field theory and rheological constitutive models, the distribution of graft copolymer was successfully estimated. It was found that large amount of copolymer had detached from the interfaces and formed micelles in the matrix. Both the block copolymer micelles in matrix and the block copolymers at the interface contribute to the suppression of coarsening in polymer blend, but play their roles at different stages of droplet coalescence. In droplet morphology, the micelles mainly hinder the approaching of droplets. © 2014 American Institute of Chemical Engineers AIChE J, 61: 285–295, 2015     

共混型高分子梯度材料在水面上的形成研究

以烷基聚噻吩（PAT-6）和聚醋酸乙烯酯（PVAc）共混液为原料通过浇注和注射方式分别在水面和空气中干燥成型,考察成型样品断面组成结构变化。     

Characterisation of [(1−x)PMMA-xPVdF] polymer blend electrolyte with Li ion

The possible use of polymeric materials in thin-film solid electrolytes for battery systems, fuel cells, sensors and other electrochemical applications has stimulated worldwide interest in metal salt solvating macromolecules. Polymer electrolyte membranes comprising of poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF) and lithium perchlorate are prepared using a solvent casting technique. Polymer blends have been characterised by FTIR and XRD studies to determine the molecular environment for the conducting ions. The role of interaction between polymer hosts on conductivity is discussed using the results of ac impedance studies. The ionic conductivity is presented as a function of temperature and PVdF content. Room temperature conductivity of 3.14×10⁻⁵ S cm⁻¹ has been obtained for the [0.25PMMA/0.75PVdF]-LiClO₄ polymer complex.