Mechanical properties of thin sol-gel films

This thesis presents a study of the mechanical properties of thin films. The main aim was to determine the properties of sol-gel derived coatings. These films are used in a range of different applications and are known to be quite porous. Very little work has been carried out in this area and in order to study the mechanical properties of sol-gel films, some of the work was carried out on magnetron sputtered metal coatings in order to validate the techniques developed in this work. The main part of the work has concentrated on the development of various bending techniques to study the elastic modulus of the thin films, including both a small scale three-point bending, as well as a novel bi-axial bending technique based on a disk resting on three supporting balls. The bending techniques involve a load being applied to the sample being tested and the bending response to this force being recorded. These experiments were carried out using an ultra micro indentation system with very sensitive force and depth recording capabilities. By analysing the result of these forces and deflections using existing theories of elasticity, the elastic modulus may be determined. In addition to the bi-axial bending study, a finite element analysis of the stress distribution in a disk during bending was carried out. The results from the bi-axial bending tests of the magnetron sputtered films was confirmed by ultra micro indentation tests, giving information of the hardness and elastic modulus of the films. It was found that while the three point bending method gave acceptable results for uncoated steel substrates, it was very susceptible to slight deformations of the substrate. Improvements were made by more careful preparation of the substrates in order to avoid deformation. However the technique still failed to give reasonable results for coated specimens. In contrast, biaxial bending gave very reliable results even for very thin films and this technique was also found to be useful for determination of the properties of sol-gel coatings. In addition, an ultra micro indentation study of the hardness and elastic modulus of sol-gel films was conducted. This study included conventionally fired films as well as films ion implanted in a range of doses. The indentation tests showed that for implantation of H⁺ ions at doses exceeding 3x10¹⁶ ions/cm², the mechanical properties closely resembled those of films that were conventionally fired to 450°C.

Mathematical modelling of the drying of sol gel microspheres

This thesis presents a mathematical model of the evaporation of colloidal sol droplets suspended within an atmosphere consisting of water vapour and air. The main purpose of this work is to investigate the causes of the morphologies arising within the powder collected from a spray dryer into which the precursor sol for Synroc™ is sprayed. The morphology is of significant importance for the application to storage of High Level Liquid Nuclear Waste. We begin by developing a model describing the evaporation of pure liquid droplets in order to establish a framework. This model is developed through the use of continuum mechanics and thermodynamic theory, and we focus on the specific case of pure water droplets. We establish a model considering a pure water vapour atmosphere, and then expand this model to account for the presence of an atmospheric gas such as air. We model colloidal particle-particle interactions and interactions between colloid and electrolyte using DLVO Theory and reaction kinetics, then incorporate these interactions into an expression for net interaction energy of a single particle with all other particles within the droplet. We account for the flow of material due to diffusion, advection, and interaction between species, and expand the pure liquid droplet models to account for the presence of these species. In addition, the process of colloidal agglomeration is modelled. To obtain solutions for our models, we develop a numerical algorithm based on the Control Volume method. To promote numerical stability, we formulate a new method of convergence acceleration. The results of a MATLAB™ code developed from this algorithm are compared with experimental data collected for the purposes of validation, and further analysis is done on the sensitivity of the solution to various controlling parameters.

Assembly of sol-gel-grown $Li _{(x)} CoO_{2}$ nanocrystals through electromagnetic irradiation

We report the fabrication of assembled nanostructures from the pre-synthesized nanocrystals building blocks through optical means of exciton formation and dissociation. We demonstrate that Li (x) CoO2 nanocrystals assemble to an acicular architecture, upon prolonged exposure to ultraviolet-visible radiation emitted from a 125 W mercury vapor lamp, through intermediate excitation of excitons. The results obtained in the present study clearly show how nanocrystals of various materials with band gaps appropriate for excitations of excitons at given optical wavelengths can be assembled to unusual nanoarchitectures through illumination with incoherent light sources. The disappearance of exciton bands due to Li (x) CoO2 phase in the optical spectrum of the irradiated film comprising acicular structure is consistent with the proposed mechanism of exciton dissociation in the observed light-induced assembly process. The assembly process occurs through attractive Coulomb interactions between charged dots created upon exciton dissociation. Our work presents a new type of nanocrystal assembly process that is driven by light and exciton directed.

Some studies on TiO2 films deposited by sol-gel technique

TiO2 films are extensively used in various applications including optical multi-layers, sensors, photo catalysis, environmental purification, and solar cells etc. These are prepared by both vacuum and non-vacuum methods. In this paper, we present the results on TiO2 thin films prepared by a sol-gel spin coating process in non-aqueous solvent. Titanium isopropoxide is used as TiO2 precursor. The films were annealed at different temperatures up to 3000 C for 5 hours in air. The influence of the various deposition parameters like spinning speed, spinning time and annealing temperature on the thickness of the TiO2 films has been studied. The variation of film thickness with time in ambient atmosphere was also studied. The optical, structural and morphological characteristics were investigated by optical transmittance-reflectance measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM) respectively. The refractive index and extinction coefficient of the films were determined by envelope technique and spectroscopic ellipsometry. TiO2 films exhibited high transparency (92%) in the visible region with a refractive index of 2.04 at 650 nm. The extinction coefficient was found to be negligibly small. The X-ray diffraction analysis showed that the TiO2 film deposited on glass substrate changes from amorphous to crystalline (anatase) phase with annealing temperature above 2500 C. SEM results show that the deposited films are uniform and crack free.

Hybrid Sol-Gel Combustion Synthesis of Nanoporous Anatase

Nanoporous anatase with a thin interconnected filmlike morphology has been synthesized in a single step by coupling a nonhydrolytic condensation reaction of a Ti precursor with a hybrid sol-gel combustion reaction. The method combines the advantages of a conventional sol-gel method for the formation of porous structures with the high crystallinity of the products obtained by combustion methods to yield highly crystalline, phase-pure nanoporous anatase. The generation of pores is initiated by the formation of reverse micelles in a polymeric polycondensation product, which expand during heating, leading to larger pores. A reaction scheme involving a complex formation and nonhydrolytic polycondensation reaction with ester elimination leads to the formation of ail extended Ti-O-Ti network. The effect of process parameters, such as temperature and relative ratio of cosurfactants, on phase formation has been studied. The possibility of band gap engineering by controlled doping during synthesis and the possibility of attachment of molecular/nanoparticle sensitizers provide opportunities for easy preparation of photoanodes for solar cell applications.

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol-gel route

Sol-gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn1-xLixO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400-500 degrees C. Ferroelectricity in Zn0.85Li0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C-V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P-s) and coercive field were 0.15 mu C/cm(2) and 20 kV/cm, respectively, confirming the presence of ferroelectricity.

Poly-ols Based Sol-Gel Synthesis of Zinc Oxide Thin Films

We demonstrate that the structural and optical properties of a sol-gel deposited zinc oxide thin film can be tuned by varying the composition of the sol, consisting of ethylene glycol and glycerol. A systematic study of the effect of the composition of sol on the mean grain size, thickness, and defect density of the zinc oxide film is presented. About 20% glycerol content in the sol is observed to improve the quality of the film, as evaluated by X-ray diffraction and photoluminescence studies. Thus, optimizing the composition of the sol for about 60 nm thick ZnO film using 20% glycerol resulted in the zinc oxide film that is about 80% transparent in visible spectrum, exhibiting electrical resistivity of about 18 Omega cm and field-effect mobility of 0.78 cm(2)/(V s). (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3515894] All rights reserved.

Sol-gel derived, magnesium based ionically conducting composites

Composite ionic conductors based on magnesium salts and sol-gel derived silicate-tetraethylene glycol hybrids have been synthesized. The structure of these materials has been studied by FT-IR, FT-Raman, Si-29 and C-13 NMR and XRD techniques. The composite systems can be best described as diphasic with silicate as filters in the organic phase that provides solubility of the ionic dispersants. The ionic interactions in the matrix are clearly observed in the FT-Raman spectra. The ionic conductivity is determined to be of the order of 10(-7) to 10(-5) S cm(-1) at room temperature for MgCl2 and Mg(ClO4)(2) salts respectively. The conductivity reaches 10(-4) and 10(-3) S cm(-1) at 80degreesC respectively.

Sol-Gel Transition in Dispersions of Layered Double-Hydroxide Nanosheets

Surfactant-intercalated layered double-hydroxide solid Mg-Al LDH-dodecyl sulfate (DDS) undergoes rapid and facile delamination to its ultimate constituent, single sheets of nanometer thickness and micrometer size, in a nonpolar solvent such as toluene to form stable dispersions. The delaminated nanosheets are electrically neutral because the surfactant chains remain tethered to the inorganic layer even on exfoliation. With increasing volume fraction of the solid, the dispersion transforms from a free-flowing sol to a solidlike gel. Here we have investigated the sol-gel transition in dispersions of the hydrophobically modified Mg-Al LDH-DDS in toluene by rheology, SAXS, and (1)H NMR measurements. The rheo-SAXS measurements show that the sharp rise in the viscosity of the dispersion during gel formation is a consequence of a tactoidal microstructure formed by the stacking of the nanosheets with an intersheet separation of 3.92 nm. The origin and nature of the attractive forces that lead to the formation of the tactoidal structure were obtained from 1D and 2D (1)H NMR measurements that provided direct evidence of the association of the toluene solvent molecules with the terminal methyl of the tethered DDS surfactant chains. Gel formation is a consequence of the attractive dispersive interactions of toluene molecules with the tails of DDS chains anchored to opposing Mg-Al LDH sheets. The toluene solvent molecules function as molecular ``glue'' holding the nanosheets within the tactoidal microstructure together. Our study shows how rheology, SAXS, and NMR measurements complement each other to provide a molecular-level description of the sol-gel transition in dispersions of a hydrophobically modified layered double hydroxide.

Perovskite phase transformation in 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) nanoparticles derived by sol-gel

Fabrication of 0.65Pb(Mg1/3Nb2./3)O-3-0.35PbTiO(3) (PMN-PT) nanoparticles with an average size of about 40 nm and their phase transformation behavior from pyrochlore to perovskite phase is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PMN-PT which was dried and partially calcined at 450 degrees C for 1 h to decompose organics and bring down the free energy barrier for perovskite crystallization and then finally annealed in the temperature range 600 to 700 degrees C. Annealed at around 700 degrees C for 1 h, PMN-PT gel powder exhibited nanocrystalline morphology with perovskite phase as confirmed by the transmission electron microscopy and X-ray diffraction techniques. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3677974]

Antimicrobial Properties of Nanostructured TiO2 Plus Fe Additive Thin Films Synthesized by a Cost-Effective Sol-Gel Process

We prepared thin films composed of pure TiO2 or TiO2 with an Fe additive (at concentrations of 0.2-0.8 wt%) via a simple and cost effective sol gel process, and tested their antifungal properties (against Candida albicans (MTCC-1637), Candida tropicalis (MTCC-184), Candida parapsilosis (MTCC-2509), and Candida glabrata (MTCC-3019) and antibacterial properties (against Staphylococcus faecalis (NCIM-2604) Staphylococcus epidermidis (NCIM-2493), Staphylococcus aureus (NCIL-2122), and Bacillus subtilis (NCIM-2549)). The films were deposited on glass and Si substrates and subjected to annealing at 400 degrees C for 3 h in ambient air. The film structural and morphological properties were investigated by X-ray photoelectron spectroscopy profilometry and scanning electron microscopy, respectively. Antifungal and antibacterial tests were conducted using the drop test method. Among the species examined, Candida albicans (MTCC-1637), and Staphylococcus aureus (NCIL-2122) showed complete colony formation inhibition after exposure for 4 h for the TiO2 loaded with 0.8 wt% Fe thin films. These results indicate that increasing the Fe concentration increased the antimicrobial activity, with complete inhibition of colony formation after 4 h exposure.

Sol-gel Processed Cu2SnS3 Films for Photovoltaics

Cu2SnS3 films have been processed by the sol-gel route. Differential Scanning Calorimetry (DSC) study was done to observe the phase transformations and to ascertain the deposition temperature. X-ray diffraction (XRD) confirms the phase formation of Cu2SnS3. The texture coefficient analysis shows the preferential orientation of the (112) facet. Scanning electron microscopy reveals the morphology of the film Energy Dispersive Spectroscopy (EDS) was used for compositional studies. Raman spectrum shows the peaks corresponding to the tetragonal phase of Cu2SnS3.