Mechanical properties of interfacial films formed by lysozyme self-assembly at the air-water interface

We present the first characterization of the mechanical properties of lysozyme films formed by self-assembly at the air-water interface using the Cambridge interfacial tensiometer (CIT), an apparatus capable of subjecting protein films to a much higher level of extensional strain than traditional dilatational techniques. CIT analysis, which is insensitive to surface pressure, provides a direct measure of the extensional stress-strain behavior of an interfacial film without the need to assume a mechanical model (e.g., viscoelastic), and without requiring difficult-to-test assumptions regarding low-strain material linearity. This testing method has revealed that the bulk solution pH from which assembly of an interfacial lysozyme film occurs influences the mechanical properties of the film more significantly than is suggested by the observed differences in elastic moduli or surface pressure. We have also identified a previously undescribed pH dependency in the effect of solution ionic strength on the mechanical strength of the lysozyme films formed at the air-water interface. Increasing solution ionic strength was found to increase lysozyme film strength when assembly occurred at pH 7, but it caused a decrease in film strength at pH 11, close to the pI of lysozyme. This result is discussed in terms of the significant contribution made to protein film strength by both electrostatic interactions and the hydrophobic effect. Washout experiments to remove protein from the bulk phase have shown that a small percentage of the interfacially adsorbed lysozyme molecules are reversibly adsorbed. Finally, the washout tests have probed the role played by additional adsorption to the fresh interface formed by the application of a large strain to the lysozyme film and have suggested the movement of reversibly bound lysozyme molecules from a subinterfacial layer to the interface.

Formation of droplets from the liquid wall film passing through the inlet port of a spark ignition engine

The available literature has been surveyed to determine the parameters affecting fuelling requirements of spark ignition engines and their relation to engine performance and emissions. Theories and experiment relating to two phase and multi-component flows have also been examined and the techniques employed in the measurement of droplet sizes and liquid wall films have been reviewed. Following preliminary steady flow visualisation experiments to examine the trajectories of droplets discharging from the valve port an extensive practical investigation of the spectrum of droplet sizes formed by the break up of the wall film has produced results which have been correlated in terms of the important fuel and airflow parameters. It is concluded that the Sauter mean diameter of droplets formed by the break up of the wall film will vary between 70 and 150 m, depending on the operating conditions of the engine. The spectra of droplet sizes measured show that a significant proportion of the total mass of the wall film breaks into drops which will be too large to burn completely and, by comparison with measurements of unburned hydrocarbon emissions from engines supplied with a homogeneous mixture of air and gaseous hydrocarbons, it is concluded that the droplets from the wall film are likely to increase emissions by 50%.

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300°C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400°C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.

The structural and piezoresponse properties of c-axis-oriented Aurivillius phase Bi5Ti3FeO15 thin films deposited by atomic vapor deposition

The deposition by atomic vapor deposition of highly c-axis-oriented Aurivillius phase Bi 5Ti 3FeO 15 (BTFO) thin films on (100) Si substrates is reported. Partially crystallized BTFO films with c-axis perpendicular to the substrate surface were first deposited at 610°C (8 excess Bi), and subsequently annealed at 820°C to get stoichiometric composition. After annealing, the films were highly c-axis-oriented, showing only (00l) peaks in x-ray diffraction (XRD), up to (0024). Transmission electron microscopy (TEM) confirms the BTFO film has a clear layered structure, and the bismuth oxide layer interleaves the four-block pseudoperovskite layer, indicating the n 4 Aurivillius phase structure. Piezoresponse force microscopy measurements indicate strong in-plane piezoelectric response, consistent with the c-axis layered structure, shown by XRD and TEM.

Room temperature electromechanical and magnetic investigations of ferroelectric Aurivillius phase Bi5Ti3(FexMn1−x)O15 (x = 1 and 0.7) chemical solution deposited thin films

Aurivillius phase thin films of Bi5Ti3(FexMn1−x)O15 with x = 1 (Bi5Ti3FeO15) and 0.7 (Bi5Ti3Fe0.7Mn0.3O15) on SiO2-Si(100) and Pt/Ti/SiO2-Si substrates were fabricated by chemical solution deposition. The method was optimized in order to suppress formation of pyrochlore phase Bi2Ti2O7 and improve crystallinity. The structuralproperties of the films were examined by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. Optimum crystallinity and pyrochlore phase suppression was achieved by the addition of 15 to 25 mol. % excess bismuth to the sols. Based on this study, 17.5 mol. % excess bismuth was used in the preparation of Bi2Ti2O7-free films of Bi5Ti3FeO15 on SrTiO3(100) and NdGaO3(001) substrates, confirming the suppression of pyrochlore phase using this excess of bismuth. Thirty percent of the Fe3+ ions in Bi5Ti3FeO15 was substituted with Mn3+ ions to form Bi2Ti2O7-free thin films of Bi5Ti3Fe0.7Mn0.3O15 on Pt/Ti/SiO2-Si, SiO2-Si(100), SrTiO3(100), and NdGaO3(001) substrates. Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films on Pt/Ti/SiO2-Si and SiO2-Si(100) substrates were achieved with a higher degree of a-axis orientation compared with the films on SrTiO3(100) and NdGaO3(001) substrates. Room temperature electromechanical and magnetic properties of the thin films were investigated in order to assess the potential of these materials for piezoelectric,ferroelectric, and multiferroic applications. Vertical piezoresponse force microscopy measurements of the films demonstrate that Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films are piezoelectric at room temperature. Room temperature switching spectroscopy-piezoresponse force microscopy measurements in the presence and absence of an applied bias demonstrate local ferroelectric switching behaviour (180°) in the films. Superconducting quantum interference device magnetometry measurements do not show any room temperature ferromagnetic hysteresis down to an upper detection limit of 2.53 × 10−3 emu; and it is concluded, therefore, that such films are not mutiferroic at room temperature. Piezoresponse force microscopy lithography images of Bi5Ti3Fe0.7Mn0.3O15thin films are presented.

Design and Implementation of Tools for STM Studies in UHV and at the Solid-Liquid Interface

This thesis presents details of the design and development of novel tools and instruments for scanning tunneling microscopy (STM), and may be considered as a repository for several years' worth of development work. The author presents design goals and implementations for two microscopes. First, a novel Pan-type STM was built that could be operated in an ambient environment as a liquid-phase STM. Unique features of this microscope include a unibody frame, for increased microscope rigidity, a novel slider component with large Z-range, a unique wiring scheme and damping mechanism, and a removable liquid cell. The microscope exhibits a high level of mechanical isolation at the tunnel junction, and operates excellently as an ambient tool. Experiments in liquid are on-going. Simultaneously, the author worked on designs for a novel low temperature, ultra-high vacuum (LT-UHV) instrument, and these are presented as well. A novel stick-slip vertical coarse approach motor was designed and built. To gauge the performance of the motor, an in situ motion sensing apparatus was implemented, which could measure the step size of the motor to high precision. A new driving circuit for stick-slip inertial motors is also presented, that o ffers improved performance over our previous driving circuit, at a fraction of the cost. The circuit was shown to increase step size performance by 25%. Finally, a horizontal sample stage was implemented in this microscope. The build of this UHV instrument is currently being fi nalized. In conjunction with the above design projects, the author was involved in a collaborative project characterizing N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on Au(111) films. STM was used to characterize Au substrate quality, for both commercial substrates and those manufactured via a unique atomic layer deposition (ALD) process by collaborators. Ambient and UHV STM was then also used to characterize the NHC/Au(111) films themselves, and several key properties of these films are discussed. During this study, the author discovered an unexpected surface contaminant, and details of this are also presented. Finally, two models are presented for the nature of the NHC-Au(111) surface interaction based on the observed film properties, and some preliminary theoretical work by collaborators is presented.

Refractometry Studies of the Optical Properties of Polymer Films and the Development of Polymer Coated Refractive Index Sensors

Sensors for real-time monitoring of environmental contaminants are essential for protecting ecosystems and human health. Refractive index sensing is a non-selective technique that can be used to measure almost any analyte. Miniaturized refractive index sensors, such as silicon-on-insulator (SOI) microring resonators are one possible platform, but require coatings selective to the analytes of interest. A homemade prism refractometer is reported and used to characterize the interactions between polymer films and liquid or vapour-phase analytes. A camera was used to capture both Fresnel reflection and total internal reflection within the prism. For thin-films (d = 10 μm - 100 μm), interference fringes were also observed. Fourier analysis of the interferogram allowed for simultaneous extraction of the average refractive index and film thickness with accuracies of ∆n = 1-7 ×10-4 and ∆d < 3-5%. The refractive indices of 29 common organic solvents as well as aqueous solutions of sodium chloride, sucrose, ethylene glycol, glycerol, and dimethylsulfoxide were measured at λ = 1550 nm. These measurements will be useful for future calibrations of near-infrared refractive index sensors. A mathematical model is presented, where the concentration of analyte adsorbed in a film can be calculated from the refractive index and thickness changes during uptake. This model can be used with Fickian diffusion models to measure the diffusion coefficients through the bulk film and at the film-substrate interface. The diffusion of water and other organic solvents into SU-8 epoxy was explored using refractometry and the diffusion coefficient of water into SU-8 is presented. Exposure of soft baked SU-8 films to acetone, acetonitrile and methanol resulted in rapid delamination. The diffusion of volatile organic compound (VOC) vapours into polydimethylsiloxane and polydimethyl-co-polydiphenylsiloxane polymers was also studied using refractometry. Diffusion and partition coefficients are reported for several analytes. As a model system, polydimethyl-co-diphenylsiloxane films were coated onto SOI microring resonators. After the development of data acquisition software, coated devices were exposed to VOCs and the refractive index response was assessed. More studies with other polymers are required to test the viability of this platform for environmental sensing applications.

Solid-liquid interactions in microscale structures and devices

Liquid-solid interactions become important as dimensions approach mciro/nano-scale. This dissertation focuses on liquid-solid interactions in two distinct applications: capillary driven self-assembly of thin foils into 3D structures, and droplet wetting of hydrophobic micropatterned surfaces. The phenomenon of self-assembly of complex structures is common in biological systems. Examples include self-assembly of proteins into macromolecular structures and self-assembly of lipid bilayer membranes. The principles governing this phenomenon have been applied to induce self-assembly of millimeter scale Si thin films into spherical and other 3D structures, which are then integrated into light-trapping photovoltaic (PV) devices. Motivated by this application, we present a generalized analytical study of the self-folding of thin plates into deterministic 3D shapes, through fluid-solid interactions, to be used as PV devices. This study consists of developing a model using beam theory, which incorporates the two competing components — a capillary force that promotes folding and the bending rigidity of the foil that resists folding into a 3D structure. Through an equivalence argument of thin foils of different geometry, an effective folding parameter, which uniquely characterizes the driving force for folding, has been identified. A criterion for spontaneous folding of an arbitrarily shaped 2D foil, based on the effective folding parameter, is thus established. Measurements from experiments using different materials and predictions from the model match well, validating the assumptions used in the analysis. As an alternative to the mechanics model approach, the minimization of the total free energy is employed to investigate the interactions between a fluid droplet and a flexible thin film. A 2D energy functional is proposed, comprising the surface energy of the fluid, bending energy of the thin film and gravitational energy of the fluid. Through simulations with Surface Evolver, the shapes of the droplet and the thin film at equilibrium are obtained. A critical thin film length necessary for complete enclosure of the fluid droplet, and hence successful self-assembly into a PV device, is determined and compared with the experimental results and mechanics model predictions. The results from the modeling and energy approaches and the experiments are all consistent. Superhydrophobic surfaces, which have unique properties including self-cleaning and water repelling are desired in many applications. One excellent example in nature is the lotus leaf. To fabricate these surfaces, well designed micro/nano- surface structures are often employed. In this research, we fabricate superhydrophobic micropatterned Polydimethylsiloxane (PDMS) surfaces composed of micropillars of various sizes and arrangements by means of soft lithography. Both anisotropic surfaces, consisting of parallel grooves and cylindrical pillars in rectangular lattices, and isotropic surfaces, consisting of cylindrical pillars in square and hexagonal lattices, are considered. A novel technique is proposed to image the contact line (CL) of the droplet on the hydrophobic surface. This technique provides a new approach to distinguish between partial and complete wetting. The contact area between droplet and microtextured surface is then measured for a droplet in the Cassie state, which is a state of partial wetting. The results show that although the droplet is in the Cassie state, the contact area does not necessarily follow Cassie model predictions. Moreover, the CL is not circular, and is affected by the micropatterns, in both isotropic and anisotropic cases. Thus, it is suggested that along with the contact angle — the typical parameter reported in literature quantifying wetting, the size and shape of the contact area should also be presented. This technique is employed to investigate the evolution of the CL on a hydrophobic micropatterned surface in the cases of: a single droplet impacting the micropatterned surface, two droplets coalescing on micropillars, and a receding droplet resting on the micropatterned surface. Another parameter which quantifies hydrophobicity is the contact angle hysteresis (CAH), which indicates the resistance of the surface to the sliding of a droplet with a given volume. The conventional methods of using advancing and receding angles or tilting stage to measure the resistance of the micropatterned surface are indirect, without mentioning the inaccuracy due to the discrete and stepwise motion of the CL on micropillars. A micronewton force sensor is utilized to directly measure the resisting force by dragging a droplet on a microtextured surface. Together with the proposed imaging technique, the evolution of the CL during sliding is also explored. It is found that, at the onset of sliding, the CL behaves as a linear elastic solid with a constant stiffness. Afterwards, the force first increases and then decreases and reaches a steady state, accompanied with periodic oscillations due to regular pinning and depinning of the CL. Both the maximum and steady state forces are primarily dependent on area fractions of the micropatterned surfaces in our experiment. The resisting force is found to be proportional to the number of pillars which pin the CL at the trailing edge, validating the assumption that the resistance mainly arises from the CL pinning at the trailing edge. In each pinning-and-depinning cycle during the steady state, the CL also shows linear elastic behavior but with a lower stiffness. The force variation and energy dissipation involved can also be determined. This novel method of measuring the resistance of the micropatterned surface elucidates the dependence on CL pinning and provides more insight into the mechanisms of CAH.

Comb-like acrylic-based polymer latexes containing nano-sized crystalline or liquid crystalline domains

306 p.

Direct visualization of magnetic-field-induced magnetoelectric switching in multiferroic Aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi6Ti2.8Fe1.52Mn0.68O18, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi6Ti2.99Fe1.46Mn0.55O18, via the liquid injection chemical vapor deposition technique. High-resolution magnetic measurements reveal a considerably higher in-plane ferromagnetic signature than CSD grown films (MS = 24.25 emu/g (215 emu/cm3), MR = 9.916 emu/g (81.5 emu/cm3), HC = 170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in-plane magnetic field cycle, where increased volumes (8.6 to 14% compared with 4 to 7% for the CSD-grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.

Formulation of ionogel, hydrogel and films using a cellulose rich solid obtained from Pinus radiata

The purpose of my internship, carried out during my Erasmus period at the Complutense University of Madrid, was focused on the formulation of ionogels and hydrogels for the obtainment of films with high lignin content, and on their characterization measuring their antibacterial properties. For biomass formulation I used lignocellulosic biomass (Pinus Radiata) as raw material and ionic liquid as solvent. The two ionic liquids proposed were: 1-ethyl-3-methylimidazoliumdimethylphosphate [Emim][DMP] and 1-ethyl-3-methylimidazoliumdiethylphosphate [Emim][DEP]. The two-starting cellulose-rich solids were obtained from Pinus radiata wood that had been submitted to an organosolv process, to reduce its lignin content to fifteen (ORG15) and twenty per cent (ORG20). Having two ionic liquids and two solids available, the first phase of the project was devoted to the screening of both solids in both ionic liquids. Through this, it was possible to identify that only the [Emim][DMP] ionic liquid fulfils the purpose. It was also possible to discard the cellulose-rich solid ORG20 because its dissolution in the ionic liquid was not possible (after the time fixed) and, additionally, a Pinus radiata cellulose-rich solid bleached with hydrogen peroxide and containing ten per cent of lignin (ORG10B) was included in the screening. After screening, a total of five ionogels were subsequently formulated: two gels were formulated with the starting raw material ORG15 (with 1% and 1.75% cellulose, respectively) and three with ORG10B (with 1%, 1.75% and 3% cellulose, respectively). Five hydrogels were obtained from the ionogels. Rheological tests were performed on each ionogel and hydrogel. Finally, films were formulated from hydrogels and they were analysed by antibacterial testing to see if they could be applied as food packaging. In addition, antioxidant and properties such as opacity and transparency were also studied.

Thermodynamics of hydrogen absorption in Mg thin films and multilayers studied by electrochemical method

Electrochemical hydrogen loading is a technique used to produce and study the hydrogenation in metals starting from a liquid solution containing water. It is a possible alternative to another, well-established technique which loads hydrogen starting from its gas phase. In this work, the electrochemical method is used to understand the fundamental thermodynamics of hydrogen loading in constraint systems such as thin films on substrates, and possibly distinguish the role of interfaces, stresses and microstructure during the hydrogenation process. The systems under study are thin films of Pd, Mg/Pd, and Ti/Mg multilayers. Possible future technological applications may be in the field of hydrogen storage and hydrogen sensors. Towards the end, the experimental setup is modified by introducing an automatic relay. This change leads to improvements in the data analysis and in the attainable information on the kinetics of the systems.

On The Distinct Molecular Architectures Of Dipping- And Spray-lbl Films Containing Lipid Vesicles.

The introduction of spraying procedures to fabricate layer-by-layer (LbL) films has brought new possibilities for the control of molecular architectures and for making the LbL technique compliant with industrial processes. In this study we show that significantly distinct architectures are produced for dipping and spray-LbL films of the same components, which included DODAB/DPPG vesicles. The films differed notably in their thickness and stratified nature. The electrical response of the two types of films to aqueous solutions containing erythrosin was also different. With multidimensional projections we showed that the impedance for the DODAB/DPPG spray-LbL film is more sensitive to changes in concentration, being therefore more promising as sensing units. Furthermore, with surface-enhanced Raman scattering (SERS) we could ascribe the high sensitivity of the LbL films to adsorption of erythrosin.

Angiogenic Effects Of Cryosurgery With Liquid Nitrogen On The Normal Skin Of Rats, Through Morphometric Study.

Cryosurgery is an efficient therapeutic technique used to treat benign and malignant cutaneous diseases. The primary active mechanism of cryosurgery is related to vascular effects on treated tissue. After a cryosurgical procedure, exuberant granulation tissue is formed at the injection site, probably as a result of angiogenic stimulation of the cryogen and inflammatory response, particularly in endothelial cells. To evaluate the angiogenic effects of freezing, as part of the phenomenon of healing rat skin subjected to previous injury. Two incisions were made in each of the twenty rats, which were divided randomly into two groups of ten. After 3 days, cryosurgery with liquid nitrogen was performed in one of incisions. The rats' samples were then collected, cut and stained to conduct histopathological examination, to assess the local angiogenesis in differing moments and situations. It was possible to demonstrate that cryosurgery, in spite of promoting cell death and accentuated local inflammation soon after its application, induces quicker cell proliferation in the affected tissue and maintenance of this rate in a second phase, than in tissue healing without this procedure. These findings, together with the knowledge that there is a direct relationship between mononuclear cells and neovascularization (the development of a rich system of new vessels in injury caused by cold), suggest that cryosurgery possesses angiogenic stimulus, even though complete healing takes longer to occur. The significance level for statistical tests was 5% (p<0,05).