Nous présentons, ici, l'adaptation d'un procédé technologique de dépôt de par jet de matière, communément appelé jet d'encre, pour la réalisation de profil de phase sur un verre pixellisé. L'étude des phénomènes complexes, mis en jeu dans le procédé jet d'encre, nous a permis d'identifier et de comprendre les interactions fortes entre les propriétés physico-chimiques des liquides fonctionnels et les contraintes technologiques des têtes d'impression. Ainsi, le contrôle des paramètres d'impression nous a permis d'optimiser la formation des gouttes éjectées. Dans un second temps, l'étude des problématiques de remplissage des microstructures pixellisées a été abordée. Différentes stratégies d'impression ont été proposées pour limiter l'impact des défauts d'impression rencontrés. Un procédé informatique de tramage a ensuite été développé, pour définir un profil de phase et gérer spatialement la volumétrie des dépôts. Les étapes de scellement et de planarisation des films microstructurés remplis ont également été abordées ainsi que les difficultés liées à leur mise en oeuvre. Enfin, un exemple de réalisation d'une lentille de Fresnel plane par procédé jet d'encre et sa caractérisation optique ont été détaillées, montrant ainsi le travail de développement réalisé lors de la thèse. / The adaptation of a technological material deposition process, named inkjet printing, is presented, here, in order to realize refractive index profiles for the pixellisation of corrective lenses. The study of the complex phenomena, involved in inkjet process, has enabled us to identify and understand the strong interactions between the physico-chemical properties of functional liquids and the technological constraints of printheads. This work allowed us to control printing parameters and optimize the drop formation process. Secondly, the study of problems related to the filling of microstructures has been approached. Various printing strategies have been proposed to limit the impact of printing errors encountered and a software has been developed for the project, allowing to define a refractive index profile and manage spatially the ejected volumes. Then, the sealing and the "planarization" processes of the filled microstructured films have been illustrated and the difficulties connected to their implementation were detailed. Finally, an example of optical microdevice was presented. Thus, the realization by inkjet printing process and the optical characterization of a flat Fresnel lens were detailed to illustrate the development realized during these works.

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03 - 0.8 ng for the GC-MS and between 0.03 - 2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Inkjet printing promises to be an invaluable technique for processing organic solar cells with key advantages such as low material consumption, freedom of design and compatibility with different types of flexible substrates making it suitable for large-area production. However, one concern about inkjet printed organic solar cells is the common use of chlorinated solvents during the ink formulation process. While chlorinated solvents suit the inkjet printing process due to their high boiling points, suitable viscosity, and excellent solubility of organic donor and acceptor compounds, they still pose some risks for both human health and the environment, excluding them from being the ultimate choice for large-area production. As a step towards commercialization of OPV, we demonstrated the possibility to close the laboratory to fabrication gap, through the engineering of environmentally friendly inks, using a blend of non-halogenated benzene derivatives solvents optimized to meet the viscosity and surface tension requirements for the inkjet printing process. Starting from using the non-fullerene acceptor O-IDTBR combined with the commercially available donor polymer P3HT we obtained solar cell device with efficiency up to 4.73% - the best efficiency achieved by the P3HT:O-IDTBR system processed with all non-halogenated solvents via inkjet printing. We also delivered highly transparent active layer with device power conversion efficiency of up to 10% with a highly efficient blend of polymer donor PTB7-Th in combination with the ultranarrow band gap NFA IEICO-4F, using hydrocarbons solvent. Lastly, we demonstrated both high efficiency, transparency, and stability by presenting a novel approach based on NFAs consisting of lowering the donor:acceptor ratio in the photoactive layer ink formulations, resulting in more stable devices with comparable power conversion efficiencies to those achieved by lab methods. This breakthrough in ink engineering paves the way in closing the lab-to-fab gap in organic photovoltaic using the low-cost, high throughput inkjet printing technology while considering both environmental and health-conscious mass production and device stability of organic photovoltaics.

In this work, Paper-based inkjet-printed Ultra-wide band (UWB) fractal antennas are presented. Three new designs, a combined UWB fractal monopole based on the fourth order Koch Snowflake fractal which utilizes a Sierpinski Gasket fractal for ink reduction, a Cantor-based fractal antenna which performs a larger bandwidth compared to previously published UWB Cantor fractal monopole antenna, and a 3D loop fractal antenna which attains miniaturization, impedance matching and multiband characteristics. It is shown that fractals prove to be a successful method of reducing fabrication cost in inkjet printed antennas while retaining or enhancing printed antenna performance.

This diploma thesis was focused on the preparation of self-cleaning and photocatalyticaly active titanium dioxide thin films. Transparent and porous thin layers of titanium dioxide were prepared from sol-gel containing titanium tetraisopropoxide (TTIP) as precursor with addition polyethylene glycol (PEG). Transparent thin layers of titanium dioxide were also prepared from colloidal solution titanium dioxide. The immobilization of thin titanium dioxide layers was performed by a sol-gel process on the soda lime glasses. Diffusion of sodium cation from soda lime glasses into titanium dioxide layer were blocked. Sol was deposited by printig method – micropiezo deposition. Sol and thin titanium dioxide layers were characterised by the physical-chemical method. For prepared sol viscosity, density and surface tension were measured. Thickness and hydrophilicity of titanium dioxide layers also were studied. The photocatalytic activity of the printed titanium layers were tested via the photocatalytic degradation of the 2,6-dichlorindophenol. The influence of addition PEG into the sol and influence of sol loading was studied. It was found that the addition of PEG into the sol significantly increased the photocatalytic activity of titanium dioxide layers.

The stability of inkjet print is influenced by a lot of factors. Mutual effects of these factors accelerate the print degradation. The surrounding environment in image stability plays an important role, when the prints degrade especially by the light. The degradation of inkjet prints is presented as a decrease of dye or multiple dyes. It is necessary to know the dye concentration for the dye decrease prediction in the time. This dissertation thesis deals with the study of kinetics and changes in electron and molecular structure of digital photography prints after accelerated ageing tests. The study of resistance of inkjet prints was realized on one type of media using three different sets of inks. Changes in printed colours were measured and evaluated in calibration (by PLS calibration and least squares method). On the basis of calibration the dye decrease prediction of real samples in receiving layer was evaluated. Changes in electron and molecular structure were analysed on KBr pellets by FTIR an UV-Vis spectroscopy.

Binder jetting is an additive manufacturing process in which a part is fabricated layer-by-layer using inkjet technology to selectively dispense binder into powder layers in a designated area. The approach gives this process significant advantages over other additive manufacturing processes such as lower cost, capability to print in a wide range of materials, and little to no heat applied. Although binder jetting has many advantages and has been successful implemented in various industries its overall rate of adoption is slow compared to other processes. This is largely due to poor mechanical properties and consistency in printing which stems from a poor understanding of the interaction between the binder droplets and the powder bed. This is evident as print parameters for new machines and new materials are primarily determined by trial and error. The purpose of this thesis is to report the impact of various inkjet print parameters and humidity on the printing process in binder jetting. The binder/powder interaction is complex and highly dynamic where picoliter-sized droplets impact the powder bed at velocities of 1-10 m/s. Current methods of predicting this interaction assume that it is based only on binder and powder properties. This work studies the impact of inkjet printing parameters that are often overlooked with these assumptions. The impact of droplet velocity, droplet spacing, and droplet inter-arrival time was evaluated based on single line formation and effective saturation levels when printed into various powder material and sizes. Higher droplet velocities were found to decrease effective saturation with larger droplets (92-212 pl). However, droplet velocity had a negligible impact on saturation when printing with smaller droplets from 30 m orifice (29-65 pl). Line formation was dependent on both droplet inter-arrival time and droplet spacing. Max droplet spacing correlated to the square root of inter-arrival time. These results can guide selection of printing parameters that maximize build rates and reduce defects in printed parts. As the binder/powder interaction is difficult to observe and often line formation has been used as a method of observation. However, no report relating line formation to full layer parts exists. Optimal parameters determined in line printing are used for full feature parts. In addition, the impact of ambient humidity on the printing process is studied. The direct use of parameters optimized for line printing in printing a part was shown to be ineffective. When droplet spacing, line spacing, and layer thicknesses are comparable, single and multiple layers can be formed. Over short exposure periods of powder to ambient humidity produces negligible difference however, extended exposure periods significantly reduce the saturation and increase part size. Surface roughness is identified as a possible source of printing defects. Surface roughness increases significantly when printing the first layer but decreases with successive layers. This demonstrates a strong interaction between layers. The surface roughness and effective saturation was insensitive to line and droplet spacing below 60 m. Steam powder conditioning reduces sensitivity of both surface roughness and saturation to printing parameters but causes bleeding beyond the part boundaries. Further research should include improved methods of predicting ideal printing parameters and connecting it based on geometry and parts size. Further research is needed to confirm impact of surface roughness on defects in binder jetting parts. Development of methods to control spread of binder in premoistened powder to take advantage of its potential.

Alkanethiols spontaneously assembles from solution or vapour on oxide free metal surfaces resulting in a close-packed molecular stuctures with a high degree of orientation and molecular order. In this study, inkjet printing technique is used to immobilize monolayers of alkanethiols on gold electrodes. The quality of the inkjetted monolayers are analyzed by electrochemical methods, i.e. cyclic voltammetry and electrochemical impedance spectroscopy, and by Polarization Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) which show a similar molecular quality to those produced by immersion technique, the standard technique. The kinetic and mass transfer behaviours of micro-scale structures of inkjetted monolayers, e.g. bands and dots array electrodes, are explored by electrochemical methods. The microscale inkjetted structures of monolayers are of interest in the fields of microelectronic devices (e.g. chemical and biosensors) and optoelectronic devices. Taking benefits from multichannel existing in the printhead, mixtures of SAMs are demonstrated. Mixing of monolayers differing in functional groups provides a model surface to study interface phenomena at molecular level such as ion permeation, selective chemical binding, and electron transfer kinetic.

Previous studies have shown that pullulan films are able to stabilize enzymes and other labile molecules from thermal and oxidative degradation. Solutions made with commercially available pullulan are extremely viscous and difficult to process limiting the ability to use low-cost printing systems, such as inkjet printers, to format pullulan-containing. In this work, we show that pullulan can be made printable by decreasing its chain length by acid hydrolysis. The acid hydrolysis reaction was modelled using statistical software; the molecular weight of pullulan decreased with increasing reaction time, temperature and acid concentration. Interactions between time and temperature, and temperature and acid concentration were determined to be significant to the reaction as well. The mechanical properties and oxygen permeability of films made from pullulan with different molecular weights were also measured. The films were found to have similar tensile properties and oxygen permeabilities to each other and to those obtained using native pullulan. Using a thermally unstable enzyme (acetylcholinesterase) and an easily oxidizable small molecule (indoxyl acetate) as test materials, it was found that these films have the same ability to stabilize the enzyme and to serve as an oxygen barrier, as the films made with native pullulan. It was also found that pullulan is inkjet printable as long as the molecular weight is 56 kDa. Poor jetting and clogging of the printhead was observed when pullulan with a molecular weight higher than this threshold was used. Microarray printing was also demonstrated by a printing acetylcholinesterase/pullulan in nano-sized volumes using a Dimatix inkjet printer and showing activity of the enzyme after printing and storage at ambient conditions. Proof of concept of microarray printing opens up the potential for future applications of pullulan in other high throughput applications. / Thesis / Master of Applied Science (MASc)

Bio-interface topography strongly affects the nature and efficiency of interactions with living cells and biological molecules, making hydrogels decorated with micro and nanostructures an attractive choice for a wide range of biomedical applications. Despite the distinct advantages of protein hydrogels, literature in the field has disproportionately focused on synthetic polymers to the point that most methods are inherently incompatible with proteins and heat-sensitive molecules. We report the development of multiple biomolecule-friendly technologies to construct microstructured protein and bacteriophage (bacterial virus) hydrogels. Firstly, ordered and sphericity-controllable microbumps were obtained on the surface of protein hydrogels using polystyrene microporous templates. Addition of protein nanogels resulted in the hierarchical nano-on-micro morphology on the microbumps, exhibiting bacterial repellency 100 times stronger than a flat hydrogel surface. The developed microstructures are therefore especially suitable for antifouling applications. The microstructures created on protein hydrogels paved the way for applying honeycomb template on proteinous bacterial viruses. We developed a high-throughput method to manufacture isolated, homogenous, pure and hybrid phage microgels. The crosslinked phages in each phage-exclusive microgel self-organized and exhibited a highly-aligned nanofibrous texture. Sprays of hybrid microgels loaded with potent virulent phage effectively reduced heavy loads of multidrug resistant Escherichia coli O157:H7 on food products by 6 logs. / Thesis / Doctor of Philosophy (PhD) / Bacteriophages (bacterial viruses), also known as phages, are natural bacteria predators. These viruses act as direct missiles, each phage targeting limited groups of bacteria. In addition, phages are an endless resource for self-propagating nanoparticles that can be used as building blocks for new material. I developed a platform for manufacturing a large quantity of microscale beads made of millions of phages. These micro-beads can be sprayed on fresh produce and meat to remove bacterial contamination (with the added benefit of not affecting taste or smell). I also printed phages on substrates, like an ink. The printed phage ink evolved into a patented technology for designing phage coatings on surfaces with very high surface area, like the small structures on our fingers. This phage coating was successfully used to test the existence of bacteria in liquids.