Synthesis of High-Value Bio-Based Polyamide 12,36 Microcellular Foams with Excellent Dimensional Stability and Shape Recovery Properties.

The search for alternatives to petroleum-based thermoplastic polyamide elastomers (TPAEs) has recently drawn great interest. In this study, a bio-massed TPAE, PA12,36, was synthesized using 1,12-dodecanediamine (DDA) and fatty dimer acid (FDA, PripolTM1009) precursors via catalyst and solvent-free melt polycondensation. The molecular structure and molecular weight of the PA12,36 were characterized by 1H NMR, FTIR, and GPC. PA12,36 displayed a low melting temperature of 85.8 °C, an initial degradation temperature of 425 °C, and a glass-transition temperature of 30.4 °C, whereas it sustained satisfactory tensile strength (10.0 MPa) and superior strain at break (1378%). Furthermore, PA12,36 was foamed by supercritical CO2, and the cell size, cell density, and porosity were determined. The entangled long-chained FDA component generated a physically crosslinked network, which promoted the melt viscosity of PA12,36 against elongations of foam cell growth and increased foamability significantly. As a result, uniform structured cellular foams with a cell diameter of 15-24 µm and high cell density (1011 cells/cm3-1012 cells/cm3) were successfully achieved. The foaming window was widened from 76 to 81 °C, and the expansion ratio was increased from 4.8 to 9.6. Additionally, PA12,36 foam with a physically crosslinked structure presented a better creep shape recovery percentage (92-97.9%) and sturdier dimensional stability. This bio-based PA12,36 foam is a promising candidate to replace petroleum-based thermoplastic elastomer foams for engineering applications, particularly shoe soles.

Synthesis and Characterization of Size-Controlled Titania Nanorods through Double Surfactants.

A synthetic technique based on a two-step sol-gel hydrothermal method using cetyltrimethylammonium bromide (CTAB) and triblock copolymer PEO106-PPO70-PEO106 (F127) as double surfactants with the assistance of three amines (ethylamine (EA), diethylamine (DEA), and triethylamine (TEA)) for fabrications of anatase titania nanorods is proposed. The formation and growth mechanisms of TiO2 crystals are described. We discovered that crystal size reduces with an increase in the number of alkyl substituents on the nitrogen of amines because the steric hindrance of the bulky alkyl substituent around nitrogen suppresses the nucleation and crystal growth rate. The size of titania from 80 to 220 nm is modulated with concentrations of EA, DEA, and TEA. The amines are considered as catalysts for morphological evolution of TiO2 crystals. The results indicate that the incorporation of double surfactants (F127-CTAB) has a dual role, acting as a chelating agent for titania against external forces and a capping agent inhibiting the three-dimensional growth of TiO2 crystals.

Characterization of Solvent-Treated PEDOT:PSS Thin Films with Enhanced Conductivities.

The conducting polymer of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is one of the most important and intensively investigated organic conducting materials. The PEDOT:PSS water dispersions with various concentrations of poly (4-styrenesulfonic acid) solution (PSSAS) were synthesized by 3,4-ethylenedioxythiophene (EDOT) in the presence of water. The fabrication of the solvent-treated PEDOT:PSS films through spin coating and solvent treatment processes was achieved with a solvent of pure water mixed with acetone (or MeOH, EtOH) in a ratio of 50:50. Moreover, both the organic solvent and water have synergetic effects while the PSS and PEDOT-attached PSS segments will form a coil-like and a linear (or extended-coil) structure, respectively. That may induce a stacking of the linear and planar PEDOT-attached PSS segments, which favors the formation of a crystalline phase. Finally, the maximum electrical conductivity of the PEDOT:PSS thin films with solvent treatment was investigated by means of X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) images. Furthermore, we aimed to explain the synergetic effects of phase separation of the PEDOT:PSS thin films by both the organic solvent and water.

Reduction of nitrobenzene with alkaline ascorbic acid: Kinetics and pathways.

Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO2(-)) of NB has a +III oxidation state of the N atom and tends to gain electrons. The effect of alkaline pH ranging from 9 to 13 was initially assessed and the results demonstrated that the solution pH, when approaching or above the pKa2 of AA (11.79), would increase reductive electron transfer to NB. The rate equation for the reactions between NB and AA at pH 12 can be described as r=((0.89±0.11)×10(-4) mM(1-(a+b))h(-1))×[NB](a=1.35±0.10)[AA](b=0.89±0.01). The GC/MS analytical method identified nitrosobenzene, azoxybenzene, and azobenzene as NB reduction intermediates, and aniline (AN) as a final product. These experimental results indicate that the alkaline AA reduction of NB to AN mainly proceeds via the direct route, consisting of a series of two-electron or four-electron transfers, and the condensation reaction plays a minor route. Preliminary evaluation of the remediation of spiked NB contaminated soils revealed that maintenance of alkaline pH and a higher water to soil ratio are essential for a successful alkaline AA application.

High-Performance and Stable Gel-State Dye-Sensitized Solar Cells Using Anodic TiO2 Nanotube Arrays and Polymer-Based Gel Electrolytes.

Highly ordered and vertically oriented TiO2 nanotube (NT) arrays were synthesized with potentiostatic anodization of Ti foil and applied to fabricate gel-state dye-sensitized solar cells (DSSCs). The open structure of the TiO2 NT facilitates the infiltration of the gel-state electrolyte; their one-dimensional structural feature provides effective charge transport. TiO2 NTs of length L=15-35 µm were produced on anodization for periods of t=5-15 h at a constant voltage of 60 V, and sensitized with N719 for photovoltaic characterization. A commercially available copolymer, poly(methyl methacrylate-co-ethyl acrylate) (PMMA-EA), served as a gelling agent to prepare a polymer-gel electrolyte (PGE) for DSSC applications. The PGE as prepared exhibited a maximum conductivity of 4.58 mS cm(-1) with PMMA-EA (7 wt %). The phase transition temperature (Tp) of the PGE containing PMMA-EA at varied concentrations was determined on the basis of the viscosities measured at varied temperatures. Tp increased with increasing concentration of PMMA-EA. An NT-DSSC with L=30 µm assembled using a PGE containing PMMA-EA (7 wt %) exhibited an overall power conversion efficiency (PCE) of 6.9%, which is comparable with that of a corresponding liquid-type device, PCE=7.1%. Moreover, the gel-state NT-DSSC exhibited excellent thermal and light-soaking enduring stability: the best device retained ∼90% of its initial efficiency after 1000 h under 1 sun of illumination at 50 °C, whereas its liquid-state counterpart decayed appreciably after light soaking for 500 h.

Femtosecond excitonic relaxation dynamics of perovskite on mesoporous films of Al2O3 and NiO nanoparticles.

The excitonic relaxation dynamics of perovskite adsorbed on mesoporous thin films of Al2O3 and NiO upon excitation at 450 nm were investigated with femtosecond optical gating of photoluminescence (PL) via up-conversion. The temporal profiles of emission observed in spectral region 670-810 nm were described satisfactorily with a composite consecutive kinetic model and three transient components representing one hot and two cold excitonic relaxations. All observed relaxation dynamics depend on the emission wavelength, showing a systematic time-amplitude correlation for all three components. When the NiO film was employed, we observed an extent of relaxation proceeding through the non-emissive surface state larger than through the direct electronic relaxation channel, which quenches the PL intensity more effectively than on the Al2O3 film. We conclude that perovskite is an effective hole carrier in a p-type electrode for NiO-based perovskite solar cells showing great performance.

Hybrid Titania Photoanodes with a Nanostructured Multi-Layer Configuration for Highly Efficient Dye-Sensitized Solar Cells.

To construct a hybrid titania photoanode containing nanoparticles and nanorods of varied size in a multilayer (ML) configuration for dye-sensitized solar cells, the essence of our ML design is a bilayer system with additional layers of nanorods of well-controlled size inserted between the transparent and the scattering layers to enhance the light-harvesting capability for photosensitizers with small absorptivity, such as Z907. We measured charge-extraction and intensity-modulated photoelectric spectra to show the advantages of one-dimensional nanorods with an improved electron-transport property and an upward shift of the potential band edge; a favorable ML configuration was constructed to have a cascade potential feature for feasible electron transport from long nanorods, to normal nanorods, to small nanoparticles. On the basis of the ML system reported herein, we demonstrate how the performance of a Z907 device is improved to attain η ∼10%, which is a milestone for its future commercialization.

Size-controlled anatase titania single crystals with octahedron-like morphology for dye-sensitized solar cells.

A simple hydrothermal method with titanium tetraisopropoxide (TTIP) as a precursor and triethanolamine (TEOA) as a chelating agent enabled growth in the presence of a base (diethylamine, DEA) of anatase titania nanocrystals (HD1-HD5) of controlled size. DEA played a key role to expedite this growth, for which a biphasic crystal growth mechanism is proposed. The produced single crystals of titania show octahedron-like morphology with sizes in a broad range of 30-400 nm; a typical, extra large, octahedral single crystal (HD5) of length 410 nm and width 260 nm was obtained after repeating a sequential hydrothermal treatment using HD3 and then HD4 as a seed crystal. The nanocrystals of size ~30 nm (HD1) and ~300 nm (HD5) served as active layer and scattering layer, respectively, to fabricate N719-sensitized solar cells. These HD devices showed greater V(OC) than devices of conventional nanoparticle (NP) type; the overall device performance of HD attained an efficiency of 10.2% power conversion at a total film thickness of 28 µm, which is superior to that of a NP-based reference device (η = 9.6%) optimized at a total film thickness of 18-20 µm. According to results obtained from transient photoelectric and charge extraction measurements, this superior performance of HD devices relative to their NP counterparts is due to the more rapid electron transport and greater TiO(2) potential.