Novel engineered proteins for mechanomaterials

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Film formation mechanism uncovered in 2D/3D mixed-dimensional lead halide perovskites

2D layered metal halides can be added to 3D perovskites to improve the long-term stability of hybrid perovskite solar cells. The presence of the low-dimensional material alters the film formation mechanism. In this issue of Chem, Kanatzidis and collaborators investigate in situ the crystallization mechanism of mixed-dimensional 2D/3D lead-based perovskite films

Role of the Processing Solvent on the Electrical Conductivity of PEDOT:PSS

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most studied conductive polymers, holding great potential in many applications such as thermoelectric generators, solar cells, and memristors. Great efforts have been invested in trying to improve its mechanical and electrical properties and to elucidate the structure-property relationship. In this work, a systematic and quantitative study of the effect of solvent polarity and solution processing on the film structure and conductivity is presented. By using grazing-incidence wide-angle X-ray scattering (GIWAXS) together with atomic force microscopy (AFM), the importance of the quality of the PEDOT crystal packing is highlighted as a key factor to reach improved electrical conductivity, rather than the overall degree of crystallinity. Moreover, the (re)structuring mechanisms occurring during the film formation and film exposure processes are also studied by in situ GIWAXS. Different intermediate precursor stages and different pathways to reach improved crystallinity are reported depending on the used solvent. The structural results are interpreted looking at the solvent nature and the PSS/solvent affinity. With this contribution, a guidance is hoped to be given not only on how to improve the PEDOT:PSS electrical conductivity, but also on how to tune the film structural or electrical property for different applications

Contribution of Ex-Situ and In-Situ X-ray Grazing Incidence Scattering Techniques to the Understanding of Quantum Dot Self-Assembly:A Review

Quantum dots are under intense research, given their amazing properties which favor their use in electronics, optoelectronics, energy, medicine and other important applications. For many of these technological applications, quantum dots are used in their ordered self-assembled form, called superlattice. Understanding the mechanism of formation of the superlattices is crucial to designing quantum dots devices with desired properties. Here we review some of the most important findings about the formation of such superlattices that have been derived using grazing incidence scattering techniques (grazing incidence small and wide angle X-ray scattering (GISAXS/GIWAXS)). Acquisition of these structural information is essential to developing some of the most important underlying theories in the field

Proton conducting ABA triblock copolymers with sulfonated poly(phenylene sulfide sulfone) midblock obtained via copper-free thiol-click chemistry dagger

A series of charged ABA triblock copolymers having sulfonated poly(phenylene sulfide sulfone) (sPSS) as B-block and polystyrene (PS) as A-block have been successfully synthesized using copper-free thiol-click chemistry. One-pot sequential radical addition-fragmentation chain transfer (RAFT) polymerization followed by functionalization with a perfluorinated chain extender (decafluorobiphenyl, DFBP) is used to prepare the PS blocks which are later cliked to the charged sPSS mid-block, synthetized using nucleophilic aromatic substitution polymerization. The proposed synthetic approach ensures good control over the composition of the resulting ABA block copolymers allowing synthesis of block copolymers with well-defined ion exchange capacity (IEC) and nanomorphology. The superstrong segregation regime (chi N >> 100) of these BCPs generates ordered nanostructures, spanning from spherical to lamellar. All the block copolymers are thermally stable up to 300 degrees C and are robust against swelling and wetting due to the dimensional stabilization of the ionic domains provided by the PS matrix. The relationship between proton conductivity and nanomorphology is investigated by electrochemical impedance spectroscopy (EIS), revealing the significant impact of self-assembly on the transport properties, reaching a maximum ion conductivity of 50 mS cm(-1) at 90 degrees C and 95% RH in the through-plane direction

Systematic Investigation on the Structure-Property Relationship in Isotactic Polypropylene Films Processed via Cast Film Extrusion

The effect of cast film extrusion processing conditions, such as the chill-roll temperature, temperature of the melt, and line speed, on the structure of different isotactic polypropylene homo- and random copolymers has been investigated by means of Small- and Wide-Angle X-ray Scattering (SAXS and WAXS) and correlated to stiffness and haze. Stiffness and transparency have been found to be strongly dependent on the temperature of the chill-roll. Interestingly, line speed has been found to affect the total crystallinity when the chill-roll temperature is increased, while an overall minor effect of the melt temperature was found for all cast films. The polymer characteristics, defined by the catalyst nature and comonomer content, affect the final material performance, with the single-site catalyzed grades performing better in both mechanics and optics. Haze levels were found to correlate with the mesophase content rather than to α-crystallinity and to be dependent on the domain size for all grades. The remarkably low haze levels reached by the single-site grade with higher isotacticity can arise from high nucleation rate and orientational effects, which ultimately yield smaller and smoother scattering domains

Improved energy density and charge-discharge efficiency in solution processed highly defined ferroelectric block copolymer-based dielectric nanocomposites

The development of light and flexible capacitive energy storage devices with high electrical energy densities is of crucial significance to respond to the ever-rising demands in advanced applications and electricity needs. Incorporation of high dielectric constant ceramic fillers inside the ferroelectric polymer matrix offers great potential to improve the energy density of dielectric materials. However, this approach often suffers from highly reduced breakdown strength caused by the large difference of the matrix and filler dielectric constants together with often poor dispersion of the ceramic additives inside the polymer. Here, we demonstrate a simple method for the preparation of improved polymer-based dielectric nanocomposites based on self-assembly of medium dielectric constant hafnium oxide nanorods using ferroelectric block copolymer. The prepared nanocomposites exhibit both improved discharged energy densities and charge-discharge efficiencies, whereas they preserve their function up to comparable electric fields as the pristine block copolymer. The enhancement of the properties is mostly ascribed to the formation of deeper charge traps due to nanorod induced crosslinking inside amorphous domains and the reduction of ferroelectric loss influenced by creation of an additional paraelectric phase in nanocomposites

Highly Stable Membranes of Poly(phenylene sulfide benzimidazole) Cross-Linked with Polyhedral Oligomeric Silsesquioxanes for High-Temperature Proton Transport

Poly(phenylene sulfide benzimidazole) has been synthesized and tested as a potential material for high-temperature proton transport. A high content of sulfide bonds has been implemented in the polymer chains to endow a high antioxidant capacity and, in combination with bulky benzimidazole pendant units, to significantly suppress crystallinity and thereby improve the solubility in highly polar aprotic solvents. The amorphous polymer has high thermal stability and high glass transition temperature (Tg). Freestanding, insoluble, and robust membranes were obtained via thermal cross-linking of the benzimidazole moieties with octa-glycidyl polyhedral oligomeric silsesquioxane (g-POSS). The series of hybrid networks (cPPSBi_X, with X being the g-POSS content wt %) showed excellent oxidative stability, with cPPSBi_15 having weight loss lower than 5% after 264 h in Fenton's reagent at 80 °C. Elastic moduli as high as 868 MPa with reduced strain at break (1.8%) were obtained. After doping the membranes with phosphoric acid, proton conductivity in the range of 2.3 × 10-2 S cm-1 at 180 °C was obtained, and the membranes show a stress at break of 2.3 MPa. Dimensional and mechanical stability were maintained also at high doping levels thanks to the inclusion of g-POSS which provides the resulting hybrid networks with increased free volume and high cross-link density

Revisiting the Mechanism of the Meso-to-α Transition of Isotactic Polypropylene and Ethylene-Propylene Random Copolymers

In this work, we have conducted in situ simultaneous small- and wide-angle X-ray scattering and Raman spectroscopy experiments to investigate the fundamental differences in the mechanism of the mesomorphic to α phase transition of the isotactic polypropylene homopolymer and the random ethylene-propylene copolymer. Via quantitative analysis of the results coming from the three techniques, we found that in the homopolymer, chain interlock and chain extension occur during the transition. However, these processes are not necessary for the transition to occur. Indeed, the presence of randomly distributed ethylene co-units hinders the chain interlock process in the early stages of the phase transition (T > 60 °C) and suppresses the chain elongation process at the later stages (T > 90 °C). Consequently, the mesomorphic to α-phase transition in the random copolymer occurs with inclusion of the ethylene co-units inside the crystal lattice, causing increased lateral interchain distance and larger crystalline sizes. Our results show how differences exist in the way solid phase transitions occur at the molecular scale when co-monomers are included into the macromolecular chains, leading to a better understanding of the thermal behavior of semi-crystalline polymers

Nanoscale Networks of Metal Oxides by Polymer Imprinting and Templating for Future Adaptable Electronics

While network formation is prevalent in nature, networks are generally not expected in inorganic structures. Exceptions are those cases in which surface states become important, such as nanoparticles. However, even in these cases, the morphology of these networks is difficult to control and they show a large degree of disorder. In this work, we show that highly ordered and interconnected nanoscale networks of functional metal oxides can be fabricated by a combination of polymer imprinting and polymer templating through solution processable methods. We report the fabrication of a number of functional oxide networks (i.e., BiFeO3, SrTiO3, La0.7Ca0.3MnO3, and HfO2) from solution, showing that all the oxide materials tried so far are able to follow the self-assembled network morphology dictated by the polymer structure. These networks were characterized for the overall structure by scanning electron microscopy and atomic force microscopy (AFM). Grazing incidence small angle X-ray scattering showed a good imprint quality on the mm2 scale for the combined networks, which is challenging given that multiple processing steps were involved during the fabrication. The material stoichiometries were investigated by X-ray photoemission spectroscopy and the crystal phases by grazing incidence wide angle X-ray scattering. When electronic functionality is anticipated, the networks behave as expected: conducting AFM on the La0.7Ca0.3MnO3 networks confirmed the conductive character of this composition; and piezoresponse force microscopy of the BiFeO3 network is consistent with the presence of ferroelectric behavior. These nanoscale networks show promise for future applications in adaptable electronics, such as neuromorphic computing or brain-inspired information processing.</p