Nanoindentation study of the mechanical behavior of TiO2 nanotube arrays

Titanium dioxide (TiO2) nanotube arrays are attracting increasing attention for use in solar cells, lithium-ion batteries, and biomedical implants. To take full advantage of their unique physical properties, such arrays need to maintain adequate mechanical integrity in applications. However, the mechanical performance of TiO2 nanotube arrays is not well understood. In this work, we investigate the deformation and failure of TiO2 nanotube arrays using the nanoindentation technique. We found that the load–displacement response of the arrays strongly depends on the indentation depth and indenter shape. Substrate-independent elastic modulus and hardness can be obtained when the indentation depth is less than 2.5% of the array height. The deformation mechanisms of TiO2 nanotube arrays by Berkovich and conical indenters are closely associated with the densification of TiO2 nanotubes under compression. A theoretical model for deformation of the arrays under a largeradius conical indenter is also proposed.

The in vivo fate of nanoparticles and nanoparticle-loaded microcapsules after oral administration in mice: Evaluation of their potential for colon-specific delivery

Anti-cancer drug loaded-nanoparticles (NPs) or encapsulation of NPs in colon-targeted delivery systems shows potential for increasing the local drug concentration in the colon leading to improved treatment of colorectal cancer. To investigate the potential of the NP-based strategies for colon-specific delivery, two formulations, free Eudragit® NPs and enteric-coated NP-loaded chitosan–hypromellose microcapsules (MCs) were fluorescently-labelled and their tissue distribution in mice after oral administration was monitored by multispectral small animal imaging. The free NPs showed a shorter transit time throughout the mouse digestive tract than the MCs, with extensive excretion of NPs in faeces at 5 h. Conversely, the MCs showed complete NP release in the lower region of the mouse small intestine at 8 h post-administration. Overall, the encapsulation of NPs in MCs resulted in a higher colonic NP intensity from 8 h to 24 h post-administration compared to the free NPs, due to a NP ‘guarding’ effect of MCs during their transit along mouse gastrointestinal tract which decreased NP excretion in faeces. These imaging data revealed that this widely-utilised colon-targeting MC formulation lacked site-precision for releasing its NP load in the colon, but the increased residence time of the NPs in the lower gastrointestinal tract suggests that it is still useful for localised release of chemotherapeutics, compared to NP administration alone. In addition, both formulations resided in the stomach of mice at considerable concentrations over 24 h. Thus, adhesion of NP- or MC-based oral delivery systems to gastric mucosa may be problematic for colon-specific delivery of the cargo to the colon and should be carefully investigated for a full evaluation of particulate delivery systems.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively.

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.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively. (C) 2008 Elsevier B.V. All rights reserved.

Calciothermic reduction of TiO2: A diagrammatic assessment of the thermodynamic limit of deoxidation

Calciothermic reduction of TiO2 provides a potentially low-cost route to titanium production. Presented in this article is a suitably designed diagram, useful for assessing the degree of reduction of TiO2 and residual oxygen contamination in metal as a function of reduction temperature and other process parameters. The oxygen chemical potential diagram à la Ellingham-Richardson-Jeffes is useful for visualization of the thermodynamics of reduction reactions at high temperatures. Although traditionally the diagram depicts oxygen potentials corresponding to the oxidation of different metals to their corresponding oxides or of lower oxides to higher oxides, oxygen potentials associated with solution phases at constant composition can be readily superimposed. The usefulness of the diagram for an insightful analysis of calciothermic reduction, either direct or through an electrochemical process, is discussed. Identified are possible process variations, modeling and optimization strategies.

Electrical, structural and magnetic properties of polyaniline/pTSA-TiO2 nanocomposites

Polyaniline (PANI)/para-toluene sulfonic acid (pTSA) and PANI/pTSA-TiO2 composites were prepared using chemical method and characterized by infrared spectroscopy (IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The electrical conductivity and magnetic properties were also measured. In corroboration with XRD, the micrographs of SEM indicated the homogeneous dispersion of TiO nanoparticles in bulk PANI/pTSA matrix. Conductivity of the PANI/pTSA-TiO2 was higher than the PAN[/pTSA, and the maximum conductivity obtained was 9.48 (S/cm) at 5 wt% of TiO2. Using SQUID magnetometer, it was found that PANI/pTSA was either paramagnetic or weakly ferromagnetic from 300 K down to 5 K with H-C approximate to 30 Oe and M-r approximate to 0.015 emu/g. On the other hand,PANI/pTSA-TiO2 was diamagnetic from 300 K down to about 50 K and below which it was weakly ferromagnetic. Furthermore, a nearly temperature-independent magnetization was observed in both the cases down to 50 K and below which the magnetization increased rapidly (a Curie like susceptibility was observed). The Pauli susceptibility (chi(pauli)) was calculated to be about 4.8 X 10(-5) and 1.6 x 10(-5)emug(-1) Oe(-1) K for PANI/pTSA and PANI/pTSA-TiO2, respectively.

EPR study of trap-centres produced on TiO2 particles during water photolysis

The results of an EPR investigation are presented on the paramagnetic trap-centres produced on hydrothermally prepared TiO2 particles during water photolysis at room temperature under band-gap irradiation. The trapped holes correspond to O− species adjacent to cation vacancies that are formed to compensate the hydroxyl ions in the subsurface layers. The trapped electrons are accounted for as Ti3+ in the conduction band or Ti3+ - adjoining oxygen vacancy to form shallow donor states. Although hole-centres are normally stabler than electron-centres, strongly adsorbed donor molecules reverse the stability. Concentration of hole-centres is increased by the presence of platinum on TiO2 surface and electron-centres are not detected on Pt/TiO2 during water photolysis.

Sacrificial photolysis of water on TiO2 fine powders prepared by the hydrothermal method

The often discussed role of surface hydroxylation of TiO2 particles as an essential characterestics for their photocatalytic activity can be verified by preparing TiO2 powders by hydrothermal method since hydroxylated surface layers will be better retained on these particles formed in superheated water. Thus, fine powders of TiO2 (rutile) with high degree of crystallinity are formed from titanium oxychloride in the mixed solvent of water and 2-propanol at 160–230°C and 20–120 atm. The anatase phase is produced from the same medium when sulfate ion impurity is present, with Image . TiO2 powders are washed free of anions and 2-propanol by ultrafiltration and are Pt mounted by a photochemical method. Aqueous suspensions of both forms of TiO2 neither as such nor after Pt-loading, do not produce H2 on band gap illumination whereas, H2 is generated in presence of hole scavengers such as EDTA, TEOA, sulfite or hypophosphite. The effects of hole scavenger concentration, Pt : TiO2 ratio, particulate suspension density and the nature of hole scavengers on H2 production are presented. Platinised rutile powders are equally active as anatase in sacrificial systems.

Anionic clay-Pt metal nanoparticle composite through intercalation of hexachloroplatinate in nickel zinc hydroxysalt

Nickel zinc hydroxysalt–Pt metal nanoparticle composite was prepared by intercalation of the anionic platinum complex, [PtCl6]2− in nickel zinc hydroxysalt through ion exchange reaction and subsequent reduction of the platinum complex by ethanol. Powder X-ray diffraction and microscopy studies indicate that the process of reduction of the platinum complex in the interlayer region of the anionic clay takes place topotactically without destroying the layers.

Optical and nonlinear absorption properties of Na doped ZnO nanoparticle dispersions

We report linear and nonlinear optical properties of the biologically important Na doped ZnO nanoparticle dispersions. Interesting morphological changes involving a spherical to flowerlike transition have been observed with Na doping. Optical absorption measurements show an exciton absorption around 368 nm. Photoluminescence measurements reveal exciton recombination emission, along with shallow and deep trap emissions. The increased intensity of shallow trap emission with Na doping is attributed to oxygen deficiency and shape changes associated with doping. Nonlinear optical measurements show a predominantly two-photon induced, excited state absorption, when excited with 532 nm, 5 ns laser pulses, indicating potential optical limiting applications.

Freeze-drying of ovalbumin loaded mesoporous silica nanoparticle vaccine formulation increases antigen stability under ambient conditions

Amino functionalised mesoporous silica nanoparticles (AM-41) have been identified as a promising vaccine delivery material. The capacity of AM-41 to stabilise vaccine components at ambient temperature (23–27 °C) was determined by adsorbing the model antigen ovalbumin (OVA) to AM-41 particles (OVA-41). The OVA-41 was successfully freeze-dried using the excipients 5% trehalose and 1% PEG8000. Both the immunological activity of OVA and the nanoparticle structure were maintained following two months storage at ambient temperature. The results of immunisation studies in mice with reconstituted OVA-41 demonstrated the induction of humoral and cell-meditated immune responses. The capacity of AM-41 particles to facilitate ambient storage of vaccine components without loss of immunological potency will underpin the further development of this promising vaccine delivery platform.

Polarized immune responses modulated by layered double hydroxides nanoparticle conjugated with CpG

Modulation of the immune response is an important step in the induction of protective humoral and cellular immunity against pathogens. In this study, we investigated the possibility of using a nanomaterial conjugated with the toll-like receptor (TLR) ligand CpG to modulate the immune response towards the preferred polarity. MgAl-layered double hydroxide (LDH) nanomaterial has a very similar chemical composition to Alum, an FDA approved adjuvant for human vaccination. We used a model antigen, ovalbumin (OVA) to demonstrate that MgAl-LDH had comparable adjuvant activity to Alum, but much weaker inflammation. Conjugation of TLR9 ligand CpG to LDH nanoparticles significantly enhanced the antibody response and promoted a switch from Th2 toward Th1 response, demonstrated by a change in the IgG2a:IgG1 ratio. Moreover, immunization of mice with CpG-OVA-conjugated LDH before challenge with OVA-expressing B16/F10 tumor cells retarded tumor growth. Together, these data indicate that LDH nanomaterial can be used as an immune adjuvant to promote Th1 or Th2 dominant immune responses suitable for vaccination purposes.

Photocatalytic activity of Ag-substituted and impregnated nano-TiO2

Ag-substituted (Ag sub) and Ag-impregnated (Ag imp), anatase phase nano-TiO2 have been synthesized by solution combustion technique and reduction technique, respectively. The catalysts were characterized extensively by powder XRD, TEM, XPS, FT-Raman, UV absorption, FT-IR, TGA, photoluminescence, BET surface area and isoelectric pH measurements. These catalysts were used for the photodegradation of dyes and for the selective photooxidation of cyclohexane to cyclohexanone. The photoactivities of the combustion-synthesized catalysts were compared with those of commercial Degussa P 25 (DP 25) TiO2, and Ag-impregnated DP 25 (Ag DP). For the photocatalytic degradation of dyes, unsubstituted combustion-synthesized TiO2 (CS TiO2) exhibited the highest activity, followed by 1% Ag imp and 1% Ag sub. For the photoconversion of cyclohexane, the total conversion of cyclohexane and the selectivity of cyclohexanone followed the order: 1% Ag sub > DP 25 > CS TiO2 > 1% Ag imp > 1% Ag DP. The kinetics of the photodegradation of dyes and of the photooxidation of cyclohexane were modeled using Langmuir–Hinshelwood rate equation and a free radical mechanism, respectively, and the rate coefficients were determined. The difference in activity values of the catalysts observed for these two reactions and the detailed characterization of these catalysts are described in this study.

Carbon-Supported Pt-TiO2 as a Methanol-Tolerant Oxygen-Reduction Catalyst for DMFCs

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalysts with varying at. wt ratios of Pt to Ti, namely, 1:1, 2:1, and 3:1, are prepared by the sol-gel method. The electrocatalytic activity of the catalysts toward oxygen reduction reaction (ORR), both in the presence and absence of methanol, is evaluated for application in direct methanol fuel cells (DMFCs). The optimum at. wt ratio of Pt to Ti in Pt-TiO2/C is established by fuel cell polarization, linear sweep voltammetry, and cyclic voltammetry studies. Pt-TiO2/C heattreated at 750 degrees C with Pt and Ti in an at. wt ratio of 2:1 shows enhanced methanol tolerance, while maintaining high catalytic activity toward ORR. The DMFC with a Pt-TiO2/C cathode catalyst exhibits an enhanced peak power density of 180 mW/cm(2) in contrast to the 80 mW/cm(2) achieved from the DMFC with carbon-supported Pt catalyst while operating under identical conditions. Complementary data on the influence of TiO2 on the crystallinity of Pt, surface morphology, and particle size, surface oxidation states of individual constituents, and bulk and surface compositions are also obtained by powder X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive analysis by X-ray, and inductively coupled plasm optical emission spectrometry.