Synthesis and characterization of ternary hybrid material based on poly-o-methoxyaniline and poly(ethylene oxide) in mesostructured V(2)O(5)

New hybrid composites based on mesostructured V(2)O(5) containing intercalated poly(ethylene oxide), poly-o-methoxyaniline and poly(ethylene oxide)/poly-o-methoxyaniline were prepared. The results suggest that the polymers were intercalated into the layers of the mesostructured V(2)O(5). Electrochemical studies showed that the presence of both polymers in the mesostructured V(2)O(5) (ternary hybrid) leads to an increase in total charge and stability after several cycles compared with binary hybrid composites. This fact makes this material a potential component as cathode for lithium ion intercalation and further, a promising candidate for applications in batteries.

Gas permeation in silicon-oxide/polymer (SiOx/PET) barrier films: role of the oxide lattice, nano-defects and macro-defects

We propose a model for permeation in oxide coated gas barrier films. The model accounts for diffusion through the amorphous oxide lattice, nano-defects within the lattice, and macro-defects. The presence of nano-defects indicate the oxide layer is more similar to a nano-porous solid (such as zeolite) than silica glass with respect to permeation properties. This explains why the permeability of oxide coated polymers is much greater, and the activation energy of permeation much lower, than values expected for polymers coated with glass. We have used the model to interpret permeability and activation energies measured for the inert gases (He, Ne and Ar) in evaporated SiOx films of varying thickness (13-70 nm) coated on a polymer substrate. Atomic force and scanning electron microscopy were used to study the structure of the oxide layer. Although no defects could be detected by microscopy, the permeation data indicate that macro-defects (>1 nm), nano-defects (0.3-0.4 nm) and the lattice interstices (<0.3 nm) all contribute to the total permeation. (C) 2002 Elsevier Science B.V. All rights reserved.

Dual-phase inkjet printed electrochromic layers based on PTA and WOX/TiO2 nanoparticles for electrochromic applications

Thesis submitted in Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa for the degree of Master in Materials Engineering

Field-effect transistors based on Zinc oxide nanoparticles

This work reports the development of field-effect transistors (FETs), whose channel is based on zinc oxide (ZnO) nanoparticles (NPs). Using screen-printing as the primary deposition technique, different inks were developed, where the semiconducting ink is based on a ZnO NPs dispersion in ethyl cellulose (EC). These inks were used to print electrolyte-gated transistors (EGTs) in a staggered-top gate structure on glass substrates, using a lithium-based polymeric electrolyte. In another approach, FETs with a staggered-bottom gate structure on paper were developed using a sol-gel method to functionalize the paper’s surface with ZnO NPs, using zinc acetate dihydrate (ZnC4H6O4·2H2O) and sodium hydroxide (NaOH) as precursors. In this case, the paper itself was used as dielectric. The various layers of the two devices were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared spectroscopy (FTIR), thermogravimetric and differential scanning calorimetric analyses (TG-DSC). Electrochemical impedance spectroscopy (EIS) was used in order to evaluate the electric double-layer (EDL) formation, in the case of the EGTs. The ZnO NPs EGTs present electrical modulation for annealing temperatures equal or superior to 300 ºC and in terms of electrical properties they showed On/Off ratios in the order of 103, saturation mobilities (μSat) of 1.49x10-1 cm2(Vs)-1 and transconductance (gm) of 10-5 S. On the other hand, the ZnO NPs FETs on paper exhibited On/Off ratios in the order of 102, μSat of 4.83x10- 3 cm2(Vs)-1and gm around 10-8 S.

Titanium oxide adhesion layer for high temperature annealed Si/Si3N4/TiOx/Pt/LiCoO2 battery structures

This work describes the influence of a high annealing temperature of about 700C on the Si(substrate)/Si3N4/TiOx/Pt/LiCoO2 multilayer system for the fabrication of all-solid-state lithium ion thin film microbatteries. Such microbatteries typically utilize lithium cobalt oxide (LiCoO2) as cathode material with a platinum (Pt) current collector. Silicon nitride (Si3N4) is used to act as a barrier against Li diffusion into the substrate. For a good adherence between Si3N4 and Pt, commonly titanium (Ti) is used as intermediate layer. However, to achieve crystalline LiCoO2 the multilayer system has to be annealed at high temperature. This post-treatment initiates Ti diffusion into the Pt-collector and an oxidation to TiOx, leading to volume expansion and adhesion failures. To solve this adhesion problem, we introduce titanium oxide (TiOx) as an adhesion layer, avoiding the diffusion during the annealing process. LiCoO2, Pt and Si3N4 layers were deposited by magnetron sputtering and the TiOx layer by thermal oxidation of Ti layers deposited by e-beam technique. Asdeposited and annealed multilayer systems using various TiOx layer thicknesses were studied by scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS). The results revealed that an annealing process at temperature of 700C leads to different interactions of Ti atoms between the layers, for various TiOx layer thicknesses (25–45 nm).

Transfer of ultrasmall iron oxide nanoparticles from human brain-derived endothelial cells to human glioblastoma cells.

Nanoparticles (NPs) are being used or explored for the development of biomedical applications in diagnosis and therapy, including imaging and drug delivery. Therefore, reliable tools are needed to study the behavior of NPs in biological environment, in particular the transport of NPs across biological barriers, including the blood-brain tumor barrier (BBTB), a challenging question. Previous studies have addressed the translocation of NPs of various compositions across cell layers, mostly using only one type of cells. Using a coculture model of the human BBTB, consisting in human cerebral endothelial cells preloaded with ultrasmall superparamagnetic iron oxide nanoparticles (USPIO NPs) and unloaded human glioblastoma cells grown on each side of newly developed ultrathin permeable silicon nitride supports as a model of the human BBTB, we demonstrate for the first time the transfer of USPIO NPs from human brain-derived endothelial cells to glioblastoma cells. The reduced thickness of the permeable mechanical support compares better than commercially available polymeric supports to the thickness of the basement membrane of the cerebral vascular system. These results are the first report supporting the possibility that USPIO NPs could be directly transferred from endothelial cells to glioblastoma cells across a BBTB. Thus, the use of such ultrathin porous supports provides a new in vitro approach to study the delivery of nanotherapeutics to brain cancers. Our results also suggest a novel possibility for nanoparticles to deliver therapeutics to the brain using endothelial to neural cells transfer.

Evaluation of uptake and transport of cationic and anionic ultrasmall iron oxide nanoparticles by human colon cells

Nanoparticles (NPs) are in clinical use or under development for therapeutic imaging and drug delivery. However, relatively little information exists concerning the uptake and transport of NPs across human colon cell layers, or their potential to invade three-dimensional models of human colon cells that better mimic the tissue structures of normal and tumoral colon. In order to gain such information, the interactions of biocompatible ultrasmall superparamagnetic iron oxide nanoparticles (USPIO NPs) (iron oxide core 9-10 nm) coated with either cationic polyvinylamine (aminoPVA) or anionic oleic acid with human HT-29 and Caco-2 colon cells was determined. The uptake of the cationic USPIO NPs was much higher than the uptake of the anionic USPIO NPs. The intracellular localization of aminoPVA USPIO NPs was confirmed in HT-29 cells by transmission electron microscopy that detected the iron oxide core. AminoPVA USPIO NPs invaded three-dimensional spheroids of both HT-29 and Caco-2 cells, whereas oleic acid-coated USPIO NPs could only invade Caco-2 spheroids. Neither cationic aminoPVA USPIO NPs nor anionic oleic acid-coated USPIO NPs were transported at detectable levels across the tight CacoReady? intestinal barrier model or the more permeable mucus-secreting CacoGoblet? model.

Reduction of corneal edema in endotoxin-induced uveitis after application of L-NAME as nitric oxide synthase inhibitor in rats by iontophoresis.

PURPOSE: To investigate the involvement of the cornea during endotoxin-induced uveitis (EIU) in the rat and the effect of Ngamma-nitro-L-arginine methyl ester (L-NAME) as nitric oxide synthase (NOS) inhibitor, administered by iontophoresis. METHODS: EIU was induced in Lewis rats that were killed at 8 and 16 hours after lipopolysaccharide (LPS) injection. The severity of uveitis was evaluated clinically at 16 hours, and nitrite levels were evaluated in the aqueous humor at 8 hours. Corneal thickness was measured, 16 hours after LPS injection, on histologic sections using an image analyzer. Transmission electron microscopy (TEM) was used for fine analysis of the cornea. Transcorneoscleral iontophoresis of L-NAME (100 mM) was performed either at LPS injection or at 1 and 2 hours after LPS injection. RESULTS: At 16 hours after LPS injection, mean corneal thickness was 153.7+/-5.58 microm in the group of rats injected with LPS (n=8) compared with 126.89+/-11.11 microm in the saline-injected rats (n=8) (P < 0.01). TEM showed stromal edema and signs of damage in the endothelial and epithelial layers. In the group of rats treated by three successive iontophoreses of L-NAME (n=8), corneal thickness was 125.24+/-10.36 microm compared with 146.76+/-7.52 microm in the group of rats treated with iontophoresis of saline (n=8), (P=0.015). TEM observation showed a reduction of stromal edema and a normal endothelium. Nitrite levels in the aqueous humor were significantly reduced at 8 hours by L-NAME treatment (P=0.03). No effect on corneal edema was observed after a single iontophoresis of L-NAME at LPS injection (P=0.19). Iontophoresis of saline by itself induced no change in corneal thickness nor in TEM structure analysis compared with normal rats. CONCLUSIONS: Corneal edema is observed during EIU. This edema is significantly reduced by three successive iontophoreses of L-NAME, which partially inhibited the inflammation. A role of nitric oxide in the corneal endothelium functions may explain the antiedematous effect of L-NAME.

Evaluation of uptake and transport of cationic and anionic ultrasmall iron oxide nanoparticles by human colon cells.

Nanoparticles (NPs) are in clinical use or under development for therapeutic imaging and drug delivery. However, relatively little information exists concerning the uptake and transport of NPs across human colon cell layers, or their potential to invade three-dimensional models of human colon cells that better mimic the tissue structures of normal and tumoral colon. In order to gain such information, the interactions of biocompatible ultrasmall superparamagnetic iron oxide nanoparticles (USPIO NPs) (iron oxide core 9-10 nm) coated with either cationic polyvinylamine (aminoPVA) or anionic oleic acid with human HT-29 and Caco-2 colon cells was determined. The uptake of the cationic USPIO NPs was much higher than the uptake of the anionic USPIO NPs. The intracellular localization of aminoPVA USPIO NPs was confirmed in HT-29 cells by transmission electron microscopy that detected the iron oxide core. AminoPVA USPIO NPs invaded three-dimensional spheroids of both HT-29 and Caco-2 cells, whereas oleic acid-coated USPIO NPs could only invade Caco-2 spheroids. Neither cationic aminoPVA USPIO NPs nor anionic oleic acid-coated USPIO NPs were transported at detectable levels across the tight CacoReady? intestinal barrier model or the more permeable mucus-secreting CacoGoblet? model.

Compositional influence on the electrical performance of zinc indium tin oxide transparent thin-film transistors

In this work, zinc indium tin oxide layers with different compositions are used as the active layer of thin film transistors. This multicomponent transparent conductive oxide is gaining great interest due to its reduced content of the scarce indium element. Experimental data indicate that the incorporation of zinc promotes the creation of oxygen vacancies. In thin-film transistors this effect leads to a higher threshold voltage values. The field-effect mobility is also strongly degraded, probably due to coulomb scattering by ionized defects. A post deposition annealing in air reduces the density of oxygen vacancies and improves the fieldeffect mobility by orders of magnitude. Finally, the electrical characteristics of the fabricated thin-film transistors have been analyzed to estimate the density of states in the gap of the active layers. These measurements reveal a clear peak located at 0.3 eV from the conduction band edge that could be attributed to oxygen vacancies.

Temperature dependence of the magnetization processes in Co/Al oxide/Permalloy trilayers

The magnetization process of Co/Al oxide/Py trilayers and its evolution with the temperature have been analyzed. The particular behavior of the Co layers, including the shift of the hysteresis loops and a coercivity increase with the decrease of temperature, is related with the apparition of a CoO layer at the Co/Al-oxide interface.

Compositional influence on the electrical performance of zinc indium tin oxide transparent thin-film transistors

In this work, zinc indium tin oxide layers with different compositions are used as the active layer of thin film transistors. This multicomponent transparent conductive oxide is gaining great interest due to its reduced content of the scarce indium element. Experimental data indicate that the incorporation of zinc promotes the creation of oxygen vacancies. In thin-film transistors this effect leads to a higher threshold voltage values. The field-effect mobility is also strongly degraded, probably due to coulomb scattering by ionized defects. A post deposition annealing in air reduces the density of oxygen vacancies and improves the fieldeffect mobility by orders of magnitude. Finally, the electrical characteristics of the fabricated thin-film transistors have been analyzed to estimate the density of states in the gap of the active layers. These measurements reveal a clear peak located at 0.3 eV from the conduction band edge that could be attributed to oxygen vacancies.

The Electronic Structure of Co-Sputtered Zinc Indium Tin Oxide Thin Films

Zinc indium tin oxide (ZITO) transparent conductive oxide layers were deposited via radio frequency (RF) magnetron co-sputtering at room temperature. A series of samples with gradually varying zinc content was investigated. The samples were characterized with x-ray and ultraviolet photoemission spectroscopy (XPS, UPS) to determine the electronic structure of the surface. Valence and conduction bands maxima (VBM, CBM), and work function were determined. The experiments indicate that increasing Zn content results in films with a higher defect rate at the surface leading to the formation of a degenerately doped surface layer if the Zn content surpasses 50%. Furthermore, the experiments demonstrate that ZITO is susceptible to ultraviolet light induced work function reduction, similar to what was earlier observed on ITO and TiO2 films.

Spectrometrical Monitoring of Laser Sintering Process of Ceramic Material

This thesis is done as a part of project called FuncMama that is a project between Technical Research Centre of Finland (VTT), Oulu University (OY), Lappeenranta University of Technology (LUT) and Finnish industrial partners. Main goal of the project is to manufacture electric and mechanical components from mixed materials using laser sintering. Aim of this study was to create laser sintered pieces from ceramic material and monitor the sintering event by using spectrometer. Spectrometer is a device which is capable to record intensity of different wavelengths in relation with time. In this study the monitoring of laser sintering was captured with the equipment which consists of Ocean Optics spectrometer, optical fiber and optical lens (detector head). Light from the sintering process hit first to the lens system which guides the light in to the optical fibre. Optical fibre transmits the light from the sintering process to the spectrometer where wavelengths intensity level information is detected. The optical lens of the spectrometer was rigidly set and did not move along with the laser beam. Data which was collected with spectrometer from the laser sintering process was converted with Excel spreadsheet program for result’s evaluation. Laser equipment used was IPG Photonics pulse fibre laser. Laser parameters were kept mainly constant during experimental part and only sintering speed was changed. That way it was possible to find differences in the monitoring results without fear of too many parameters mixing together and affecting to the conclusions. Parts which were sintered had one layer and size of 5 x 5 mm. Material was CT2000 – tape manufactured by Heraeus which was later on post processed to powder. Monitoring of different sintering speeds was tested by using CT2000 reference powder. Moreover tests how different materials effect to the process monitoring were done by adding foreign powder Du Pont 951 which had suffered in re-grinding and which was more reactive than CT2000. By adding foreign material it simulates situation where two materials are accidently mixed together and it was studied if that can be seen with the spectrometer. It was concluded in this study that with the spectrometer it is possible to detect changes between different laser sintering speeds. When the sintering speed is lowered the intensity level of light is higher from the process. This is a result of higher temperature at the sintering spot and that can be noticed with the spectrometer. That indicates it could be possible to use spectrometer as a tool for process observation and support the idea of having system that can help setting up the process parameter window. Also important conclusion was how well the adding of foreign material could be seen with the spectrometer. When second material was added a significant intensity level raise could be noticed in that part where foreign material was mixed. That indicates it is possible to see if there are any variations in the material or if there are more materials mixed together. Spectrometric monitoring of laser sintering could be useful tool for process window observation and temperature controlling of the sintering process. For example if the process window for specific material is experimentally determined to get wanted properties and satisfying sintering speed. It is possible if the data is constantly recorded that the results can show faults in the part texture between layers. Changes between the monitoring data and the experimentally determined values can then indicate changes in the material being generated by material faults or by wrong process parameters. The results of this study show that spectrometer could be one possible tool for monitoring. But to get in that point where this all can be made possible much more researching is needed.

Acidic dissolution of iron oxides and regeneration of a ceramic filter medium

The dewatering of iron ore concentrates requires large capacity in addition to producing a cake with low moisture content. Such large processes are commonly energy intensive and means to lower the specific energy consumption are needed. Ceramic capillary action disc filters incorporate a novel filter medium enabling the harnessing of capillary action, which results in decreased energy consumption in comparison to traditional filtration technologies. As another benefit, the filter medium is mechanically and chemically more durable than, for example, filter cloths and can, thus, withstand harsh operating conditions and possible regeneration better than other types of filter media. In iron ore dewatering, the regeneration of the filter medium is done through a combination of several techniques: (1) backwashing, (2) ultrasonic cleaning, and (3) acid regeneration. Although it is commonly acknowledged that the filter medium is affected by slurry particles and extraneous compounds, published research, especially in the field of dewatering of mineral concentrates, is scarce. Whereas the regenerative effect of backwashing and ultrasound are more or less mechanical, regeneration with acids is based on chemistry. The chemistry behind the acid regeneration is, naturally, dissolution. The dissolution of iron oxide particles has been extensively studied over several decades but those studies may not necessarily be directly applicable in the regeneration of the filter medium which has undergone interactions with the slurry components. The aim of this thesis was to investigate if free particle dissolution indeed correlates with the regeneration of the filter medium. For this purpose, both free particle dissolution and dissolution of surface adhered particles were studied. The focus was on acidic dissolution of iron oxide particles and on the study of the ceramic filter medium used in the dewatering of iron ore concentrates. The free particle dissolution experiments show that the solubility of synthetic fine grained iron oxide particles in oxalic acid could be explained through linear models accounting for the effects of temperature and acid concentration, whereas the dissolution of a natural magnetite is not so easily explained by such models. In addition, the kinetic experiments performed both support and contradict the work of previous authors: the suitable kinetic model here supports previous research suggesting solid state reduction to be the reaction mechanism of hematite dissolution but the formation of a stable iron oxalate is not supported by the results of this research. Several other dissolution mechanisms have also been suggested for iron oxide dissolution in oxalic acid, indicating that the details of oxalate promoted reductive dissolution are not yet agreed and, in this respect, this research offers added value to the community. The results of the regeneration experiments with the ceramic filter media show that oxalic acid is highly effective in removing iron oxide particles from the surface of the filter medium. The dissolution of those particles did not, however, exhibit the expected behaviour, i.e. complete dissolution. The results of this thesis show that although the regeneration of the ceramic filter medium with acids incorporates the dissolution of slurry particles from the surface of the filter medium, the regeneration cannot be assessed purely based upon free particle dissolution. A steady state, dependent on temperature and on the acid concentration, was observed in the dissolution of particles from the surface even though the limit of solubility of free iron oxide particles had not been reached. Both the regeneration capacity and efficiency, with regards to the removal of iron oxide particles, was found to be temperature dependent, but was not affected by the acid concentration. This observation further suggests that the removal of the surface adhered particles does not follow the dissolution of free particles, which do exhibit a dependency on the acid concentration. In addition, changes in the permeability and in the pore structure of the filter medium were still observed after the bulk concentration of dissolved iron had reached a steady state. Consequently, the regeneration of the filter medium continued after the dissolution of particles from the surface had ceased. This observation suggests that internal changes take place at the final stages of regeneration. The regeneration process could, in theory, be divided into two, possibly overlapping, stages: (1) dissolution of surface-adhered particles, and (2) dissolution of extraneous compounds from within the pore structure. In addition to the fundamental knowledge generated during this thesis, tools to assess the effects of parameters on the regeneration of the ceramic filter medium are needed. It has become clear that the same tools used to estimate the dissolution of free particles cannot be used to estimate the regeneration of a filter medium unless only a robust characterisation of the order of regeneration efficiency is needed.