Showing papers on "Miscibility published in 2020"

Thermodynamic Properties and Molecular Packing Explain Performance and Processing Procedures of Three D18:NFA Organic Solar Cells

Abstract: Organic solar cells (OSCs) based on D18:Y6 have recently exhibited a record power conversion efficiency of over 18%. The initial work is extended and the device performance of D18-based OSCs is compared with three non-fullerene acceptors, Y6, IT-4F, and IEICO-4Cl, and their molecular packing characteristics and miscibility are studied. The D18 polymer shows unusually strong chain extension and excellent backbone ordering in all films, which likely contributes to the excellent hole-transporting properties. Thermodynamic characterization indicates a room-temperature miscibility for D18:Y6 and D18:IT-4F near the percolation threshold. This corresponds to an ideal quench depth and explains the use of solvent vapor annealing rather than thermal annealing. In contrast, D18:IEICO-4Cl is a low-miscibility system with a deep quench depth during casting and poor morphology control and low performance. A failure of ternary blends with PC71 BM is likely due to the near-ideal miscibility of Y6 to begin with and indicates that strategies for developing successful ternary or quaternary solar cells are likely very different for D18 than for other high-performing donors. This work reveals several unique property-performance relations of D18-based photovoltaic devices and helps guide design or fabrication of yet higher efficiency OSCs.

Uncompatibilized PBAT/PLA Blends: Manufacturability, Miscibility and Properties.

Abstract: Polymer blends of poly(butylene adipate-co-terephthalate) (PBAT) and polylactide (PLA) have been drawn attention due to the application potential as packaging or agricultural films. This study aims to determine the manufacturability, miscibility and mechanical properties of uncompatibilized PBAT/PLA blends prepared using different techniques. First, PBAT and PLA are melt-blended in a wide range of ratios from 90/10 to 10/90. The compounds are then processed into pressed panels, flat films and blown films. Finally, the thermal, morphological, rheological and mechanical properties of these blends are investigated. PBAT/PLA blends have a small difference of solubility parameters, predicting theoretically good miscibility. However, they show two almost unchanged glass transition temperatures in the DSC, phase separation in SEM and two relaxation mechanisms in the Cole-Cole plot. The phase morphology varies depending on both the blend ratios and the preparation techniques. Tensile tests indicate that with increasing PLA content the elongation at break decreases. A good correlation between the elongation at break and the tear propagation resistance is found. Furthermore, the trouser tear method is proven to be more applicable to differentiate highly extensible blown films compared with the Elmendorf tear method.

Sustainable Plastics from Biomass: Blends of Polyesters Based on 2,5-Furandicarboxylic Acid

Abstract: Intending to expand the thermo-physical properties of bio-based polymers, furan-based thermoplastic polyesters were synthesized following the melt polycondensation method. The resulting polymers, namely, poly(ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), poly(butylene 2,5-furandicarboxylate) (PBF) and poly(1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PCHDMF) are used in blends together with various polymers of industrial importance, including poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), poly(L-lactic acid) (PLA) and polycarbonate (PC). The blends are studied concerning their miscibility, crystallization and solid-state characteristics by using wide-angle X-ray diffractometry (WAXD), differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEF blends show in general dual glass transitions in the DSC heating traces for the melt quenched samples. Only PPF–PEF blends show a single glass transition and a single melt phase in PLM. PPF forms immiscible blends except with PEF and PBF. PBF forms miscible blends with PCHDMF and PPF, whereas all other blends show dual glass transitions in DSC and phase separation in PLM. PCHDMF–PEF and PEN–PEF blends show two glass transition temperatures, but they shift to intermediate temperature values depending on the composition, indicating some partial miscibility of the polymer pairs.

Phase behavior and rheology of miscible and immiscible blends of linear and hyperbranched siloxane macromolecules

Abstract: It is obvious that polymers of the similar composition but with different molecular weights are miscible, but what will happen if one of them is linear and another one has branched architecture? In this paper, mixtures of linear polydimethylsiloxane (PDMS) with methyl-terminated silicone MT resins are considered. Since these resins consist of hyperbranched macromolecules with nearly spherical shape and nanoscale diameters, they are both macromolecules and colloid particles at the same time. The phase states of mixtures were studied by laser interferometry method accompanied with rheological tests. The effect of molecular weight of resins and their terminal groups on miscibility was demonstrated. The methyl-terminated resins with low molecular weight are well miscible with linear PDMS macromolecules but immiscible blends are formed in the case of resin's high molecular weight. The rheology of the blends is determined by their phase state, which depends on the ratio of components and temperature. For homogeneous resin/PDMS mixtures, a slight positive deviation of viscosity from the log-additivity rule is inherent, whereas heterogeneous blends are similar in rheological behavior to a gum. Various empirical equations are considered for describing the viscosity-composition dependence; as a result, their unification to characterize blends with different phase states was proposed.

Plasticizer Enhancement on the Miscibility and Thermomechanical Properties of Polylactic Acid-Chitin-Starch Composites.

Abstract: In previous research, a polylactic chitin starch composite was prepared without the use of a solvent to enhance the miscibility. In this study, a polylactic acid (PLA) chitin starch composite was produced with chloroform as a plasticizer in the ratio 1:10. The blending of chitin and starch with PLA ranges from 2% to 8%. Tensile strength, impact, thermogravimetry analysis-Fourier-transform infrared spectroscopy (TGA)-FTIR, and differential scanning calorimetry (DSC) were used to test the thermomechanical properties. Also, the morphological properties, water absorption, and wear rate of the material was observed. The results showed that the tensile strength, yield strength, and impact strength were improved compared to the pure polylactic acid. Also, the elastic modulus of the samples increased, but were lower compared to that of the pure polylactic acid. The result of the fractured surface morphology showed good miscibility of the blending, which accounted for the good mechanical properties recorded in the study. The thermogravimetric analysis (TGA) and derivative thermogravimetric analysis DTA show a single degradation and peak respectively, which is also shown in the glass temperature measures from the DSC analysis. The water absorption test shows that the water absorption rate increases with starch content and the wear rate recorded sample A (92% P/8% C) as the highest. The high miscibility projected was achieved with no void, with the use of chloroform as a plasticizer.

Improving the toughness and thermal resistance of polyoxymethylene/poly(lactic acid) blends : evaluation of structure – properties correlation for reactive processing

Abstract: The study focuses on the development of polyoxymethylene (POM)/poly(lactic acid) (PLA) blends with increased impact and thermal resistance. The study was conducted in two phases; in the first part, a series of unmodified blends with PLA content of 25, 50, and 75 wt.% was prepared, while the second part focused on the modification of the PLA/POM (50/50) blends. An ethylene/butyl acrylate/glycidyl methacrylate terpolymer (E/BA/GMA) elastomer (EBA) was used to improve the impact strength of the prepared blends, while reactive blending was used to improve interfacial interactions. We used a multifunctional epoxy chain extender (CE) as the compatibilizer. Static tensile tests and notched Izod measurement were used to evaluate the mechanical performance of the prepared samples. The thermomechanical properties were investigated using dynamic mechanical thermal analysis (DMTA) analysis and heat deflection temperature (HDT)/Vicat softening temperature (VST) methods. The crystallinity was measured using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXS) measurements, while the rheology was evaluated using a rotational rheometer. The paper also includes a structure analysis performed using the SEM method. The structural tests show partial miscibility of the POM/PLA systems, resulting in the perfect compatibility of both phases. The impact properties of the final blends modified by the EBA/CE system were found to be similar to pure POM resin, while the E modulus was visibly improved. Favorable changes were also noticeable in the case of the thermomechanical properties. The results of most of the conducted measurements and microscopic observations confirm the high efficiency of the reaction for PLA as well as for the modified POM/PLA mixtures.

Asymmetric Siloxane Functional Side Chains Enable High-Performance Donor Copolymers for Photovoltaic Applications.

Abstract: In this work, three benzodithiophene–benzotriazole alternated wide band gap copolymers attaching symmetric or asymmetric conjugated side chains, namely, PDBTFBTA-2T, PBDTFTBA-TSi, and PBDTFBTA-2Si, were developed for efficient nonfullerene polymer solar cells. The symmetry effect of the side chains was investigated in detail on the overall properties of these donor polymers. The results demonstrated that the introduced siloxane functional groups showed less effect on the absorption and frontier orbital levels of the prepared polymers but had a significant effect on the miscibility between these polymer donors and the nonfullerene acceptor. When increasing the content of siloxane functional groups, the miscibility of the polymer donors and Y6 would be improved, leading to the decreased domain size and more mixed domains. Interestingly, the active blend based on PBDTFTBA-TSi with asymmetric side chains exhibited more balanced miscibility, carrier mobility, and phase separation, benefiting exciton diffusion and dissociation. Therefore, a champion power conversion efficiency (PCE) of 14.18% was achieved finally in PBDTFTBA-TSi devices, which was 20.6 and 19.0% higher than the symmetric counterparts of PBTFBTA-2T devices (PCE = 11.76%) and PBDTFBTA-2Si devices (PCE = 11.92%), respectively. This work highlights that the asymmetric side-chain engineering based on siloxane functional groups is a promising design strategy for high-performance polymer donor semiconductors.

Experimental Determinations of Minimum Miscibility Pressures Using Hydrocarbon Gases and CO2 for Crude Oils from the Bakken and Cut Bank Oil Reservoirs

Abstract: Minimum miscibility pressures (MMPs) were measured at reservoir temperatures using a capillary-rise vanishing interfacial tension (VIT) technique for four crude oils collected from different format...

Understanding alcohol aggregates and the water hydrogen bond network towards miscibility in alcohol solutions: graph theoretical analysis

Abstract: Under ambient conditions, methanol and ethanol are miscible in water at all concentrations, while n-butanol is partially miscible. This is the first study to quantitatively examine the miscibility of butanol and compare with miscible alcohols by employing molecular dynamics simulations and graph theoretical analysis of three water-alcohol mixtures at various concentrations. We show how distinct alcohol aggregates are formed, thereby affecting the water structure, which established the relationship between the morphological structure of the aggregates and the miscibility of the alcohol in aqueous solution. The aggregates of methanol and ethanol in highly concentrated solutions form an extended H-bond network that intertwines well with the H-bond network of water. n-Butanol tends to self-associate and form large aggregates, while such aggregates are segregated from water. Graph theoretical analysis revealed that the alcohol aggregates of methanol and ethanol solutions have a morphological structure different from that of n-butanol, although there is no significant difference in morphology between the three pure alcohols. These two distinct alcohol aggregates are classified as water-compatible and water-incompatible depending upon their interaction with the water H-bond network, and their effect on the water structure was investigated. Our study reveals that the water-compatible network of alcohol aggregates in methanol and ethanol solutions disrupts the water H-bond networks, while the water-incompatible network of n-butanol aggregates does not considerably alter the water structure, which is consistent with the experimental results. Furthermore, we propose that miscible alcohols form water-compatible networks in binary aqueous systems while partially miscible alcohols form water-incompatible networks. The bifurcating hypothesis on the alcohol aggregation behavior in liquid water is of critical use to understand the fundamental issues such as solubility and phase separation in solution systems.

Factors Affecting the Nonsolvent-Induced Phase Separation of Cellulose from Ionic Liquid-Based Solutions.

Abstract: In the present work, we report for the first time an in-depth study of the factors influencing porous cellulose film structure formation during the nonsolvent-induced phase separation (NIPS) process from biopolymer solutions in ionic liquid-based solvents. The length of the alkyl chain of the ionic liquid's cation, the solvent/co-solvent ratio, and the type of the cellulose precursor used were found to have great influence both on cellulose solution formation and properties and to the NIPS process with water acting as nonsolvent. In the undiluted form, both studied ionic liquids proved to dissolve almost equally well the cellulose; however, due to differences in viscosities of the formed biopolymer solutions and due to differences in miscibility with water of the two ionic liquids, the used ionic liquid had a strong influence on the film's porous structure formation. The use of increasing amounts of an aprotic co-solvent, here dimethylsulfoxide, improved biopolymer solubilization and also led to the formation of a more pronounced macroporous structure during the NIPS process. The cellulose type also affected the porous structure generation during the NIPS process: with the increase of the molecular weight of the precursor, the viscosity of the formed biopolymer solution increased and the tendency to generate macroporous structures decreased.

Mechanical, morphological, thermal properties and hydrolytic degradation behavior of polylactic acid/polypropylene carbonate blends prepared by solvent casting

Abstract: The preparation of polylactic acid (PLA) and polypropylene carbonate (PPC) blend films by using the solvent casting method is to improve the properties of pure PLA. The blends' mechanical and thermal properties, morphological as well as hydrolytic degradation behavior are evaluated. The tensile test proved that the increase of PPC from 0 wt% to 75 wt% could improve the elongation of pure PLA when the graph showed a significant increase of the elongation from 10% to 1000%. Scanning Electron Microscopy (SEM) supported the significant increase in elongation of the blends when it shows a definite phase separation in 75/25 PLA/PPC, where 25% of PPC has formed islands in the PLA matrix. Differential scanning calorimetry indicates the partial miscibility of the blends where two peaks of the glass transition temperature moved towards each other when the amount of PPC increases. Fourier transform infrared (FTIR) spectroscopy revealed a possible intermolecular interaction between two polymers, which affects the miscibility of the blends. Finally, the hydrolytic degradation test indicates that the degradation started from the PLA phase and the blends' degradation rate decrease as wt% of PPC increase

Crystallization behavior of plasticized poly(lactide) film by poly( l -lactic acid)-poly(ethylene glycol)-poly( l -lactic acid) triblock copolymer

Abstract: Poly(l-lactic acid)-poly(ethylene glycol)-poly(l-lactic acid) triblock copolymer (PLLA-PEG-PLLA) prepared by simple esterification of l-lactic acid (l-LA) and diol-polyethylene glycol (diol-PEG) is proposed as an effective plasticizer for poly(lactide) film (PLA). Differential scanning calorimetry and X-ray diffraction analyses reveal improvement in PLA/PLLA-PEG-PLLA blend miscibility without PEG segment recrystallization in the PLA matrix. A comparative study on the performance of PLLA-PEG-PLLA with two different PLLA chain lengths clarifies that long PLLA-PEG-PLLA with balanced block lengths of PLLA and PEG segments performs a semicrystalline structure of PLA crystal without PEG-crystal formation, resulting in blend miscibility. This microstructure clearly induces the perfect α-form of the PLA crystal with increased degree of crystallinity to 50%. Additionally, the sufficiently long PLLA segment in triblock copolymer can get entangled with PLA chains, allowing to enhance melt strength of the PLA/long PLLA-PEG-PLLA blend. In contrast, short PLLA-PEG-PLLA is amorphous, obstructing the formation of the highly ordered PLA packing structure in the blend, and contributing to poor melt strength and mechanical weakness. Furthermore, the PLA/long PLLA-PEG-PLLA blend improves toughness with increased elongation at break to 80% while maintaining the relatively high tensile strength, as compared to that of PLA/PEG or PLA/short PLLA-PEG-PLLA films at the same blending weight ratio.