A new method for manufacturing nanostructured electrodes on glass substrates

The present paper describes a new method for manufacturing a nanostructured porous layer of TiO₂ on a conducting glass substrate for use in a dye-sensitized photoelectrochemical cell. The method involves deposition of a layer of semiconductor particles onto a conducting substrate and compression of the particle layer to form a mechanically stable, electrically conducting, and porous nanostructured film at room temperature. Photoelectrochemical characteristics and morphology of the resulting nanostructured films are presented. The potential use of the new manufacturing method in the future applications of nanostructured systems is discussed.     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

The Einstein relation in nanostructured materials: simplified theory and suggestion for experimental determination

An attempt is made to study the Einstein relation for the diffusivity–mobility ratio (DMR) in quantum wells (QWs) and quantum well wires (QWWs) of tetragonal compounds on the basis of a newly formulated electron energy spectrum taking into account the combined influences of the anisotropies in effective electron mass, the spin–orbit splitting, and the presence of crystal field splitting, respectively. The results for quantum-confined III–V compounds form a special case of our generalized analysis. The DMR has also been studied for QWs and QWWs of II–VI and IV–VI materials. Taking QWs and QWWs of CdGeAs₂, InAs, CdS and PbSe as examples, it was found that the DMR increases with increasing carrier statistics and decreasing film thickness respectively in various oscillatory manners emphasizing the influence of dimensional quantizations and the energy band constants in different cases. An experimental method of determining the DMR in nanostructures with arbitrary dispersion laws has also been suggested and the present simplified analysis is in agreement with the suggested relationship. The well-known results for nanostructures with parabolic energy bands have also been obtained as special cases from this generalized analysis under certain limiting conditions.     

A detailed analysis of ambipolar diffusion in nanostructured metal oxide films

In this paper a transport equation is derived which describes the behaviour of the nanostructured metal oxide films in a photoelectrochemical cell. It is shown that a detailed analysis of the charge compensation mechanism necessarily leads to a transport equation with characteristics similar to but logically distinct from the pure diffusion equation. The studied phenomenon was named ambipolar diffusion in the early 1950s. It takes into account the fact that the diffusion processes of ions and electrons occur at different speeds. A weak electric field therefore couples the processes together to preserve charge neutrality. The electric field in turn affects the transport resulting in a deviation from purely diffusive behaviour. However, this has not been widely recognised in the literature for nanostructured semiconductor films until very recently. In this paper a detailed analysis is presented. It is based on the assumption that the current density is solenoidal. It is shown that application of the ambipolar diffusion model to a photoelectrochemical cell based on a nanostructured metal oxide film leads to an additional term in the transport equation, rather than only a new diffusion coefficient as in earlier work. It is also shown that the boundary conditions interact closely with the equation to form a transport model.     

Synthesis and characterization of mechanical-alloyed Ti–xMg alloys

The synthesis and characterization of Ti–xMg (x=4, 9, 12, 15, 21, 24 at%) alloys using mechanical alloying was investigated. A nanometer-sized Ti–24Mg alloy was produced. During mechanical alloying, the height of the XRD peaks of the Mg in the Ti–9Mg alloy decreased, and then disappeared, whereas the Ti XRD peaks broadened, and the grain size decreased with increasing milling time. The Mg firstly dissolved in the grain boundaries of the Ti, and then diffused into the Ti grain interiors. The grain boundaries played an important role in enhancing the solid solubility of Mg in Ti. With increasing Mg content the volume fraction of grain boundaries increased, and a decrease in grain size occurred after mechanical alloying for 48 h.     

Formation of nanostructured YSZ/Ni anode with pore channels by plasma spraying

YSZ/Ni is the conventionally most used material for making the anode of a solid oxide fuel cell. Agglomerated nanostructured YSZ/NiO powders and plasma spray are applied to produce nanostructured YSZ/NiO coatings on porous support substrates. After reduction in an ambient atmosphere of 7% hydrogen and 93% argon at about 800 °C for 4 hours, a novel SOFC anode with nanostructured characteristics such as nano YSZ particles, nano Ni particles, nano pores and nano pore channels is produced. This new YSZ/Ni anode provides larger triple phase boundaries for hydrogen oxidation reactions. X-ray diffraction patterns of these YSZ/NiO coatings after 1 h of heat treatment at temperatures from 700 to 1100 °C are obtained and Scherrer analysis is conducted to study the effect of temperature on grain size. The results obtained from SEM, TEM, XRD and EDX measurements and analyses are presented in this investigation.     

Dynamic behaviour of viologen-activated nanostructured TiO2: correlation between kinetics of charging and coloration

The dynamic response of viologen-activated nanostructured titanium dioxide has been studied by means of electrical and electro-optical measurements. We show that the state of charge of the semiconductor network is the key factor mediating between the electrode potential and colouration of viologen. Theoretically, we relate the electrode potential to the statistics of occupancy of both TiO₂ nanoparticles and oxidized viologen molecules attached to the surface, on the assumption of quasi-equilibrium of Fermi levels in these contacting phases. Experimentally, we determine the statistical function from steady-state measurements (electrochemical impedance spectroscopy) of the capacitance of the semiconductor film. From this understanding we explain the main features that correlate the simultaneous voltammetry and transmittance responses. Finally, the redox process of viologen is resolved separately from the TiO₂ response by means of transmittance data.     

Broadband dielectric spectroscopy of nanostructured maleated polypropylene/polycarbonate blends prepared by in situ polymerization and compatibilization

The miscibility and molecular dynamics of nanostructured maleated polypropylene (mPP)/polycarbonate (PC) blends prepared by in situ polymerization of macrocyclic carbonates with polypropylene modified with 0.5 wt% of maleic anhydride-reactive groups were investigated over a wide range of frequencies (10⁻²-0.5 × 10⁷ Hz) at different constant temperatures using broadband dielectric spectroscopy and scanning transmission electron microscope (STEM). The molecular dynamics of the glass relaxation process of the blend (α-relaxation process) appeared at a lower temperature range compared with that of the pure PC. This shift in the molecular relaxation process is attributed to the partial miscibility of the two polymer components in the blends as previously confirmed by the morphology via STEM. Nanoscale morphologies with average domain diameters as small as 50 nm were obtained for the different blend compositions studied. The STEM photographs show that the graft mPP-g-PC prefers to locate at the interfaces as previously reported. The relaxation spectrum of pure PC and mPP/PC blends was resolved into α- and β-relaxation processes using the Havriliak-Negami equation and ionic conductivity. The dielectric relaxation parameters, such as relaxation peak broadness, maximum frequency, f_max, and dielectric strength, Δ? (for the α- and β-relaxation processes), were found to be blend composition dependent. The kinetics of the α-relaxation processes of the blends were well described by Vogel-Fulcher-Tammann (VFT) equation. The local process of PC was resolved into two relaxation processes β₁ and β₂, associated with the carbonyl groups' motion and the combined motions of carbonyl and phenylene groups, respectively. Only β₂ shifted to lower frequency in the blend while β₁ was relatively not affected by blending. The electric modulus of the blends was used to get a sufficient resolution of the different relaxation processes in the samples, i.e., α-, β-relaxation processes, ionic conductivity, and interfacial polarization. In addition, the blending method used was found to increase the d.c. conductivity without affecting the charge carrier transport mechanism, making it possible to develop novel polymer blends with tunable dielectric properties and morphology from existing polymers.     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase, photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.