Solvent- and Light-Sensitive AIEE-Active Azo Dye: From Spherical to 1D and 2D Assemblies

Fluorescent molecular assembly systems provide an exciting platform for creating stimuli-responsive nano- and microstructured materials with optical, electronic, and sensing functions. To understand the relationship between (i) the plausible molecular structures preferentially adopted depending on the solvent polarity (such as N,N-dimethylformamide [DMF], tetrahydrofuran [THF], and toluene), (ii) the resulting spectroscopic features, and (iii) self-assembled nano-, micro-, and macrostructures, we chose a sterically crowded triangular azo dye (3Bu) composed of a polar molecular core and three peripheral biphenyl wings. The chromophore changed the solution color from yellow to pink-red depending on the solvent polarity. In a yellow DMF solution, a considerable amount of the twisted azo form could be kept stable with the help of favorable intermolecular interactions with the solvent molecules. By varying the concentration of the DMF solution, the morphology of self-assembled structures was transformed from nanoparticles to micrometer-sized one-dimensional (1D) structures such as sticks and fibers. In a pink-red toluene solution, the periphery of the central ring became more planar. The resulting significant amount of the keto-hydrazone tautomer grew into micro- and millimeter-sized 1D structures. Interestingly, when THF-H2O (1:1) mixtures were stored at a low temperature, elongated fibers were stacked sideways and eventually developed into anisotropic two-dimensional (2D) sheets. Notably, subsequent exposure of visible-light-irradiated sphere samples to solvent vapor resulted in reversible fluorescence off↔on switching accompanied by morphological restoration. These findings suggest that rational selection of organic dyes, solvents, and light is important for developing reusable fluorescent materials.

Three-Dimensional Physical Simulation of Heavy Oil Exploitation by Hot Solvent Injection

To improve the thermal effects of solvents on heavy oil reservoirs and realize the combined action of multiple flooding mechanisms, such as solvent heating and extraction, without steam mixing, based on the M Block heavy oil reservoir in Canada, three sets of comparative hot solvent-assisted gravity drainage experiments under different temperatures and pressures were carried out through an indoor three-dimensional (3D) physical simulation device. The development characteristics of the solvent chamber in the hot solvent-assisted gravity drainage technology were studied under different pressures and temperatures, and the recovery factor, cumulative oil exchange rate, and solvent retention rate were analyzed. The results showed that due to the effect of gravity differentiation, the development morphology of the solvent chamber could be divided into three stages: rapid ascent, lateral expansion, and slow descent. When the temperature was constant, the reservoir pressure decreased, the recovery rate increased, the cumulative oil exchange rate increased, and the solvent retention rate decreased; when the pressure was constant, the temperature increased, the viscosity of heavy oil decreased, the recovery rate increased, the cumulative oil exchange rate increased, and the solvent retention rate was low. Additionally, the study also showed that for hot solvents in different phases, the use of hot solvent vapor not only required less injected solvent but also exhibited a high oil production rate, which shortened production time and reduced energy consumption. Moreover, the oil recovery rate was higher than 60%, the solvent retention rate was lower than 10%, and the cumulative oil exchange rate was higher than 3 t / t , which constituted better economic benefits and provided a reliable theoretical basis for onsite oilfield applications.

Enhancement of Physical Characteristics of Styrene–Acrylonitrile Nanofiber Membranes Using Various Post-Treatments for Membrane Distillation

Insufficient mechanical strength and wide pore size distribution of nanofibrous membranes are the key hindrances for their concrete applications in membrane distillation. In this work, various post-treatment methods such as dilute solvent welding, vapor welding, and cold-/hot-pressing processes were used to enhance the physical properties of styrene–acrylonitrile (SAN) nanofiber membranes fabricated by the modified electrospinning process. The effects of injection rate of welding solution and a working distance during the welding process with air-assisted spraying on characteristics of SAN nanofiber membranes were investigated. The welding process was made less time-consuming by optimizing system parameters of the electroblowing process to simultaneously exploit residual solvents of fibers and hot solvent vapor to reduce exposure time. As a result, the welded SAN membranes showed considerable enhancement in mechanical robustness and membrane integrity with a negligible reduction in surface hydrophobicity. The hot-pressed SAN membranes obtained the highest mechanical strength and smallest mean pore size. The modified SAN membranes were used for the desalination of synthetic seawater in a direct contact membrane distillation (DCMD). As a result, it was found that the modified SAN membranes performed well (>99.9% removal of salts) for desalination of synthetic seawater (35 g/L NaCl) during 30 h operation without membrane wetting. The cold-/hot-pressing processes were able to improve mechanical strength and boost liquid entry pressure (LEP) of water. In contrast, the welding processes were preferred to increase membrane flexibility and permeation.

Solvent vapor annealing for controlled pore expansion of block copolymer-assembled inorganic mesoporous films

Mesoporous inorganic thin films are promising materials architectures for a variety of high-value applications, ranging from optical coatings and purification membranes to sensing and energy storage devices. Having precise control over the structural parameters of the porous network is crucial for expanding their applicability. To this end, the use of block copolymers (BCP) as sacrificial structure-directing agents via micelle co-assembly is a particularly attractive route, since the resultant pore size is directly related to scaling laws for the radius of gyration of the pore-forming macromolecule. However, tailoring the molecular weight of the BCP via bespoke synthesis is an elaborate process that requires precise control over highly sensitive reactions conditions. Alternative methods have emerged, based on supramolecular assembly or the addition of different swelling agents, but, to-date, these present a negative impact on the structural order and pore size dispersity of the final inorganic mesoporous films. In this work, we propose a novel and effective method for control over pore size, porosity and structural order, which relies on a synergistic combination of BCP selective swelling via solvent vapor annealing (SVA) and locking of the structure by condensation of the inorganic sol-gel precursors. The results obtained in this work for TiO2 establish SVA as a new, straightforward, simple, and powerful route efor the fabrication of mesoporous thin-film materials with controllable structural characteristics.

Vertical Cylinder-to-Lamella Transition in Thin Block Copolymer Films Induced by In-Plane Electric Field

Morphological transition between hexagonal and lamellar patterns in thin polystyrene–block–poly(4-vinyl pyridine) films simultaneously exposed to a strong in-plane electric field and saturated solvent vapor is studied with atomic force and scanning electron microscopy. In these conditions, standing cylinders made of 4-vinyl pyridine blocks arrange into threads up to tens of microns long along the field direction and then partially merge into standing lamellas. In the course of rearrangement, the copolymer remains strongly segregated, with the minor component domains keeping connectivity between the film surfaces. The ordering tendency becomes more pronounced if the cylinders are doped with Au nanorods, which can increase their dielectric permittivity. Non-selective chloroform vapor works particularly well, though it causes partial etching of the indium tin oxide cathode. On the contrary, 1,4-dioxane vapor selective to polystyrene matrix does not allow for any morphological changes.

Solvent-structured PEDOT:PSS surfaces: fabrication strategies and nanoscale properties

We present the preparation of nanostructured conducting PEDOT:PSS thin films by solvent vapor annealing (SVA), using the low boiling point solvent tetrahydrofuran (THF). An Atomic Force Microscopy (AFM) study allowed the observation of distinct nanostructure development as a function of solvent exposure time. Moreover, the nanostructures’ physical properties were evaluated by nanomechanical, nanoelectrical, and nano-FTIR measurements. In this way, we were able to differentiate the local response of the developed phases and to identify their chemical nature. The combination of these techniques allowed to demonstrate that exposure to THF is a facile method to effectively and selectively modify the surface nanostructure of PEDOT:PSS, and thereafter its final properties. Moreover, our nanoscale studies provided evidence about the molecular rearrangements that PEDOT:PSS suffers during nanostructure fabrication, a fundamental fact in order to expand the potential applications of this polymer in thermoelectric and optoelectronic devices.