Facile Synthesis of a Furan–Arylamine Hole‐Transporting Material for High‐Efficiency,Mesoscopic Perovskite Solar Cells

A novel hole‐transporting molecule (F101) based on a furan core has been synthesized by means of a short, high‐yielding route. When used as the hole‐transporting material (HTM) in mesoporous methylammonium lead halide perovskite solar cells (PSCs) it produced better device performance than the current state‐of‐the‐art HTM 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD). The F101‐HTM‐based device exhibited both slightly higher J_sc (19.63 vs. 18.41 mA cm^?2) and V_oc (1.1 vs. 1.05 V) resulting in a marginally higher power conversion efficiency (PCE) (13.1 vs. 13 %). The steady‐state and time‐resolved photoluminescence show that F101 has significant charge extraction ability. The simple molecular structure, short synthesis route with high yield and better performance in devices makes F101 an excellent candidate for replacing the expensive spiro‐OMeTAD as HTM in PSCs.     

Flocculation kinetics of precipitated calcium carbonate

When the percentage of filler in paper is increased, the optical properties are improved and the production cost lowered. However, fillers weaken paper strength by decreasing the fibre–fibre bonded area. Little is known about the optimum filler floc size or filler floc properties to allow developing optimum paper characteristics. Consequently, the kinetics of aggregation of scalenohedral precipitated calcium carbonate (PCC) filler was studied using various polymers (flocculants, coagulants and dry strength agents). The sodium salt of partially hydrolysed polyvinyl formamide copolymerized with acrylic acid (PVFA/NaAA) or C-starch lead to floc sizes, less sensitive to dosage within a certain range. Results from stability ratios correlate with PCC particle size. The change in particle size measured by photometric dispersion analysis (PDA) correlates well with the change in PCC particle size measured by light scattering/diffraction. Kinetic calculations show the orthokinetic aggregation times to be consistent with the experimental PDA results. The main uncertainty in the orthokinetic times is estimating the effective shear rate. It is proposed that the bridging surface area of PCC particles, the area which can form bonds between PCC particles or aggregates, should be used to study the kinetics of PCC aggregation, and not the total or projected surface area. In polymer induced aggregation, the PCC particle size increases to a plateau value with increasing polymer dosage. Two regions are most pronounced for C-PAM, PVFA/NaAA and A-starch. Region I corresponds to bridging flocculation. Region II is where the particle size reaches a plateau, and not the expected maximum predicted by classical polymer bridging theory or charge neutralisation theory, likely because of a competition between particle aggregation and polymer adsorption.     

The role of electron photoemission in the ‘photoconductivity' of semiconducting polymers

We present the excitation profile of the transient and steady-state photoconductivity of poly(phenylene vinylene) and its soluble derivatives over a wide spectral range up to hν=6.2 eV. An apparent increase in the ‘photoconductivity' at hν>3–4 eV arises from external current generated by electron photoemission (PE). After quenching the PE by adding a gas mixture of CO₂+SF₆ (90%:10%) into the sample chamber, the bulk photoconductivity is nearly independent of photon energy in all polymers studied. The single threshold for photoconductivity is spectrally close to the onset of π–π^* absorption, a behavior that is inconsistent with a large exciton binding energy.     

Bivariate hierarchical Hermite spline quasi-interpolation

Spline quasi-interpolation (QI) is a general and powerful approach for the construction of low cost and accurate approximations of a given function. In order to provide an efficient adaptive approximation scheme in the bivariate setting, we consider quasi-interpolation in hierarchical spline spaces. In particular, we study and experiment the features of the hierarchical extension of the tensor-product formulation of the Hermite BS quasi-interpolation scheme. The convergence properties of this hierarchical operator, suitably defined in terms of truncated hierarchical B-spline bases, are analyzed. A selection of numerical examples is presented to compare the performances of the hierarchical and tensor-product versions of the scheme.     

Gelation of charged bio-nanocompartments induced by associative and non-associative polysaccharides

Vesicles composed of sodium oleate (NaO) and monoolein (MO) are adequate candidates for drug nanoencapsulation and controlled release due to their stability and perceived biocompatibility. The object of the present study is to design hydrogels based on those anionic vesicles and polymers of both non-associative and associative type. The selected macromolecules were k-carrageenan (KC), carboxymethyl cellulose (CMC) and hydrophobically modified carboxymethyl cellulose (HMCMC). While the polymer-vesicle association was probed by rheology, the influence of the polymer on the vesicle stability was monitored by cryo-TEM and calorimetric measurements. The effects of the polymer on the rheological properties of surfactant aggregate solutions clearly depend on the polymer type: the storage moduli of the polymer-vesicle mixtures, compared to the vesicles alone, increases around 2 orders of magnitude if the polymer is non-associative and 4 orders of magnitude if the macromolecule is of associative type. As the vesicles are added, the non-associative polymer networks tend to be disrupted, while the networks formed by associative polymer get more robust. These observations can be explained by fundamental changes in electrostatic/hydrophobic interactions: vesicles entrapped in KC networks convert the polysaccharide in a highly charged entity and favor high electrostatic repulsions between the chains; this encourages network collapse. The opposite picture is experienced in HMCMC systems, i.e., such network is stabilized by the presence of vesicles. This is ascribed to the enhanced hydrophobic association, compensating the electrostatic repulsions between vesicles and polymer chains.     

Melting of orbital ordering in KMgxCu1-xF3 solid solution

The long-range and short-range structures of KMgxCu1-xF3 (0 < x < 1) have been investigated by means of XRPD and EPR. Two different solid solutions are present, based on the structure of KMgF3 (for x > 0.42) and of KCuF3 (for x < 0.26), respectively, and they are separated by a biphasic zone. Positional disorder is induced by doping due to the different Cu and Mg environments. In fact, the EPR measurements have shown that the Cu environment is isotropic for x > 0.8. It shows axial symmetry for 0.45 < x < 0.70 and orthorhombic symmetry for x = 0.43. For x > 0.42, the crystallographic structure is cubic, and in absence of local disorder, a fully isotropic octahedral undistorted environment is expected for Cu. In the tetragonal structure, collective magnetic interactions arise, and a progressive EPR signal symmetrization is observed due to anisotropic exchange and to Dzialoshinsky-Moriya antisymmetric exchange processes. The mixing of triplet and singlet states induced by the above exchange mechanisms leads to the conclusion that the orbital order is melt in the x = 0.1 sample, for which the cooperative Jahn-Teller distortion is still active and the 3D magnetic order is still antiferromagnetic, as in KCuF3.     

The beneficial influence of ultrasound in the polymerization of epsilon-caprolactam to polyamide-6 (Nylon 6). Part II: additional experiment to understand the "pre-sonication effect"

Ultrasound (US) “pre-sonication effect” is the beneficial effect of US in the hydrolytic polymerization of ε-caprolactam (CL) mixtures with very low water concentrations (about 0.1–1 wt%). It appears after a mild initial treatment of the mixtures with US [17.5–20 kHz, short times (5–15 min), low temperatures (70–110 °C)] followed by heating at 220–260 °C. An explanation is proposed on the basis of the formation in mild conditions (100 °C) of low concentrations of cyclic oligomers never detected in the literature at those conditions. These, under US irradiation, produce linear amino acid oligomers, which are strong activators of polymerization when the mixture of CL and water, after US irradiation, is heated at the suitable polymerization temperature indicated above.