Porous anodic aluminium oxide (PAOX) has different practical applications (e.g. filters with uniform pore sizes, adsorbers, porous templates for functional nanomaterials), but the formation mechanism is still poorly understood. Equal-sized hexagonally ordered pores are formed during anodic oxidation of aluminium in water solutions of some acids at certain concentrations and temperatures, and comparatively high electrode potentials. Today, a limited range of pore diameters and the degree of hexagonal ordering are reached with empirically found conditions. Here, a theoretical model explaining the appearance of honeycomb structure in porous anodic alumina is presented. The proposed mechanism is based on a dissipative self-organization process, but not on the earlier accepted fieldassisted dissolution of pre-formed dense alumina. Our analysis rests on the concept that electrolyte currents near aluminium anode are organized in the same way as well-known Rayleigh-B enard convection currents. A simple yet effective way to predict pore formation in unexplored electrolytes is suggested. The validity of theoretical considerations is experimentally confirmed by the growth of hexagonally arranged porous alumina in a new electrolyte-aqueous formic acid solution.
The lack of a reliable method for theoretical prediction of nanoporous anodic alumina films obtained from non-familiar electrolytes prompted the search of a viable solution to this problem. The theory explaining the self-assembly mechanism was described in our preceding work. Here, the results of an extensive validation test are presented.
A comparative study of self-ordering behaviour of anodic alumina films fabricated in a series of diluted (down to 0.05 M) oxalic acid electrolytes allowed developing a relationship between the supporting electrolyte concentration and self-ordering voltages for the formation of porous oxide materials. Besides its practical importance, this work elucidates some fundamental principles of porous alumina formation, e.g. it suggests that the cell patterning arises from the electrohydrodynamic (EHD) convection process rather than the interfacial tension gradients near the anode surface (Marangoni-type instability).
Nanoporous anodic alumina films with long-range hexagonal order have been obtained from a series of highly diluted sulfuric acid electrolytes. A simple linear relationship was established between the selfordering voltages and acid concentrations (28, 29, and 30 V for 0.2, 0.1, and 0.05 M electrolytes, respectively). Besides establishing new self-ordering regimes, our experimental work sheds new light on some fundamental principles of honeycomb anodic alumina formation. It suggests that the spontaneous self-organization of a stable nanoscale structure originates from the electrohydrodynamic (EHD) convection rather than from Marangoni-type instability at the anode surface. Theoretical analysis displays a decreasing exponential functional relationship between electrolyte concentration and the critical values of the earlier found electrochemical analogue of Rayleigh number, which can be used for prediction of hexagonal cell pattern in currently unexplored anodizing electrolytes.
A novel molecular approach to the synthesis of polycrystalline Cu-doped ZnO rod-like nanostructures with variable concentrations of introduced copper ions in ZnO host matrix is presented. Spectroscopic (PLS, variable temperature XRD, XPS, ELNES, HERFD) and microscopic (HRTEM) analysis methods reveal the +II oxidation state of the lattice incorporated Cu ions. Photoluminescence spectra show a systematic narrowing (tuning) of the band gap depending on the amount of Cu(II) doping. The advantage of the template assembly of doped ZnO nanorods is that it offers general access to doped oxide structures under moderate thermal conditions. The doping content of the host structure can be individually tuned by the stoichiometric ratio of the molecular precursor complex of the host metal oxide and the molecular precursor complex of the dopant, Di-aquo-bis[2-(methoxyimino)-propanoato]zinc(II) 1 and -copper(II) 2. Moreover, these keto-dioximato complexes are accessible for a number of transition metal and lanthanide elements, thus allowing this synthetic approach to be expanded into a variety of doped 1D metal oxide structures.
Metallic Cr, Al, and Pt/Pd alloy have been deposited by magnetron sputtering or thermal evaporation (resistance heating or electron beam heating) onto nanoporous anodic alumina and have allowed to facilitate a cost-effective technique for manufacturing of pigment-free colored coatings on aluminum. Bright and saturated colors were achieved using the interference effect, and tuned by variation of the uniform oxide film thickness. Morphology and properties of these coatings were investigated by scanning electron microscopy (SEM) and reflectance measurements (UV/Vis/NIR spectrometry). Some optical properties of anodic alumina membranes are rather variable and strongly depend on oxidation parameters, non-stoichiometric composition, and porosity. However, the established correspondence between the film thickness, metallic coating type, and observed interference colors, allows facile, scalable, and inexpensive deposition of colored decorative and wear-resistant coatings onto aluminum and alloys surfaces.
Over the past few years, researchers have made numerous breakthroughs in the field of aluminum anodizing and faced the problem of the lack of adequate theoretical models for the interpretation of some new experimental findings. For instance, spontaneously formed anodic alumina nanofibers and petal-like patterns, flower-like structures observed under AC anodizing conditions, and hierarchical pores whose diameters range from several nanometers to sub-millimeters could be explained neither by the classical field-assisted dissolution theory nor by the plastic flow model. In addition, difficulties arose in explaining the basic indicators of porous film growth, such as the nonlinear current–voltage characteristics of electrochemical cells or the evolution of hexagonal pore patterns at the early stages of anodizing experiments. Such a conceptual crisis resulted in new multidisciplinary investigations and the development of novel theoretical models, whose evolution is discussed at length in this review work. The particular focus of this paper is on the recently developed electroconvection-based theories that allowed making truly remarkable advances in understanding the porous anodic alumina formation process in the last 15 years. Some explanation of the synergy between electrode reactions and transport processes leading to self-organization is provided. Finally, future prospects for the synthesis of novel anodic architectures are discussed.
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