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This thesis reports on the challenge of applying an innovative ‘soft-soft nanocomposite’ design strategy to establish synthesis parameters that affect the performance of coatings based upon water-borne latexes, which is driven by the environmental and legislative need to develop feasible alternatives to solvent-borne coatings. A framework emulsion polymerisation formulation to synthesise core-shell latexes with (poly[(butyl acrylate)-co-(butyl methacrylate)]) core and (poly[(butyl acrylate)-co-(butyl methacrylate)-co-(diacetone acrylamide)]) shell copolymer phases in a controlled manner was established, with high monomer conversions and approximately constant particle numbers. Retention of particle morphology in the films was confirmed using atomic force microscopy (AFM). The effect of adding adipic acid dihydrazide to the latex post-polymerisation to facilitate crosslinking of the shell phase during film formation was found to have a significant effect on the stress-strain properties of latex films. A core:shell mass ratio of 80:20 was found to be optimum in all crosslinked systems tested. Increasing the amount of crosslinking in the shell phase of the particles was found to have an effect on the large strain tensile properties of films, leading to strain hardening with reduced extension to break and higher failure stresses at higher crosslinker levels. Core phase copolymer Tg had a very significant effect upon the low strain mechanical properties, with Young’s modulus values of 5-180 MPa being accessible in the range of core Tg¬s from 5 – 25 oC, although little difference in mechanical behaviour was seen when varying the shell phase Tg from 5 – 15 oC. Adding 2 wt% methacrylic acid (MAA) to the shell phase copolymer gave an additional improvement in the low strain tensile region, with a Young’s modulus of 425 MPa being realised. However, it was found that additional amounts of MAA (up to 5 wt% in the shell phase) were deterious to film properties, with low Young’s modulus and poor extensibility. This was interpreted as being due to an increased concentration of ionomeric crosslinks restricting interparticle chain diffusion and keto-hydrazide crosslinking. Studies to evaluate the mechanical performance of soft-soft nanocomposite films compared to binder latexes used in commercial products were favourable, and showed that a high level of versatility with regards to mechanical properties is possible.

Square planar metal bis-dithiolenes are interesting targets for incorporation into electronic and optoelectronic devices as they characteristically display multiple stable redox states, coupled with strong absorption at particularly low energies. This work focuses on novel methods for the formation of thin films of metal bis-dithiolenes for incorporation into devices. The synthesis, structure and spectroscopic properties of a novel class of polymerisable heteroleptic nickel dithiolene complex, containing pendent thiophene units, [Ni(R2pipdt)(b-3ted)] are described [R = Bz (3a), iPr (3b); pipdt = piperazine- 3,2-dithione; b-3ted = bis-(3-thienyl)-1,2-ethylenedithiolene]. Electrooxidation of (3a) showed it to incorporate into a polymeric film over an electrode surface, which consisted of intact dithiolene units, by covalent linking of the pendent thienyl groups. This polymer film showed some redox activity, with the intense, low energy, absorption red-shifted by 4360 cm-1. Co-polymerisation of (3a) with thiophene yielded a highly conductive film, with the intense, low energy, absorption red-shifted to a lesser extent (3500 cm-1). The films displayed interesting optical properties, however, their use was restricted by their poor redox activity, thought to be due to poor ion transport through the films. The synthesis of two novel dithiolene ligand systems, containing pendent polymerisable indolyl groups (mi-5edt and mi-5hdt), are described, and their incorporation into complexes investigated for nickel [Ni(mi-5edt)2 (6) and Ni(mi-5hdt)2 (8)], and copper f[Cu(mi-5edt)2][TMA] ([7][TMA]) and [Cu(mi-5hdt)2][TMA] ([9][TMA])g investigated [(mi-5edt) = 1-(N-methylindol-5-yl)-ethane-1,2-dithiolate and (mi-5hdt) = 1- (N-methylindol-5-yl)-hex-1-ene-1,2-dithiolate, TMA = tetramethylammonium]. Each complex was characterised in terms of its structure, redox and optical properties, and the effect of the ligand design, and the metal centre, compared. The complexes of nickel were shown to yield polymer films under electrooxidative conditions, through covalent linking of the indolyl groups, with superior redox activity to 3a, and with an equally intense low energy absorption. The monoanionic complexes of copper were shown to deposit, under electrooxidative conditions, as neutral molecular films that were otherwise unobtainable by conventional solution techniques. The incorporation of the more soluble novel indolyl functionalised nickel dithiolene 8 into electronic devices was investigated. Electrochromic devices were formed using poly- 8 as the active layer. The devices were able to switch their optical absorption profile at 860 nm through three absorbing states by application of a suitable potential difference across the film. Field-effect transistors were fabricated using a molecular film of 8 as the active layer. The devices showed ambipolar charge transport properties, though with a bias for n-channel operation, with mobilities μ ≈ 1 x 10-4 cm2V-1s-1. Photovoltaic devices were formed from a blended film of 8 with P-3HT and with MDMO-PPV [P-3HT = regioregular poly-3-hexylthiophene, MDMO-PPV = poly(2-methoxy-5- (3',7'-dimethyloctyloxy)-1,4-phenylene-vynylene)]. 8 was shown to contribute to the photocurrent at wavelengths beyond the polymer component, thus harvesting more visible light, however efficiencies below 0.1 % suggested inefficient charge transport by 8 in the film. Structurally continuous films of Ni(b-3ted)2 (10) could be formed by a process of electrodeposition. The formed films displayed conductivities 40 times greater than for conventional solution cast films. By a detailed study of the level of residual ion doping, the molecular packing, and the morphology of the films, this improved performance was attributed to the formation of a more dense polycrystalline array, with larger crystallites, which formed good electronic contact with the electrodes, and with each other. This electrodeposition technique was used to fabricate field-effect transistors from 10. The devices showed poor mobilities (μ ≈ 1 x 10 -8 cm2V-1s-1), owing to the poor intermolecular overlap of the dithiolene units in the solid-state, but suggested this technique to be suitable for a wide range of semiconductors, with more favourable electronic properties, as an alternative to conventional vapour or solution deposition.

Metal-oxide thin films are used in a wide variety of electronic devices. Although many techniques have been developed to deposit thin films of metal oxides, there is still a need for alternative cost- and energy-effective deposition methods. Deposition of metal oxide thin films from aqueous solutions of all-inorganic metal salts is a viable method that meets these needs. Although many aqueous-deposited metal-oxide thin films have been successfully incorporated into functioning devices, many of the mechanisms that occur as precursors transition to metal oxides are not well understood. The work presented in this dissertation is primarily concerned with examining the processes that occur as metal oxide thin films form from spin-deposited aqueous precursor solutions with a particular focus on the role of H2O in these processes. Chapter I summarizes methods for thin film deposition, and describes the use of aqueous metal salt solutions as viable precursors for the deposition of metal oxide thin films. Chapter II investigates the precursor chemistry, film-formation processes and properties of LaAlO3 thin films deposited from aqueous precursors. This chapter also serves as general guide to the processes that occur as metal-oxide thin films form from spin-deposited aqueous precursors. Chapters III and IV focus on the effects of H2O(g) during spin-deposition of precursor thin films and during the annealing process in which precursors are converted to metal oxides, respectively. The presence of H2O(g) during spin-deposition has a striking effect on the thickness of the resulting thin films and also affects the elemental gradient and density profiles. During annealing, H2O(g) reduces the temperatures at which counterions are expelled and influences the metal-hydroxide framework formation and its condensation to a metal oxide. The data also indicate that H2O(g) enhances diffusion of gaseous byproducts from within the films. Chapter V focuses on precursor concentration and its impact on the thermal evolution of thin films. The processes involved in the conversion of precursors to metal oxide thin films occur at lower temperatures as precursor concentration decreases. Although this is likely in part due to thickness effects, concentration-dependent precursor speciation may also be involved in lowering the temperatures at which films densify. / 2019-02-17

<p>The objective of this master thesis was to investigate the possibility to measure the gain in stiffness of the dry coating due to film formation of latex with a Dynamic Mechanic Thermal Analyzer (DMTA). This could tell when and to which extent the latex forms a film after the drying process.</p><p>Two latices with different Tg was used for the experiments, one with a Tg of 36°C, denoted hard, and the one with a Tg of 8°C, denoted soft. The hard latex was used to make coating samples that would not form a film when dried at room temperature and the soft latex was used as a reference to the coating with hard latex since it would form a film at room temperature.</p><p>It was shown that a gain in stiffness due to film formation of latex in coating can be measured with a DMTA. It was also shown that that the film forming of latex in coatings depend on time, temperature and the history of the sample. Further investigations were carried out to try to determine the time for film formation to be completed at a certain temperature.. These investigations showed that this type of trials cannot be carried out in a DMTA directly since the stiffness seemed to increase monotonically during a very ling time. This might be due to the rearrangements in the pigment structure that might affect the gain in stiffness. Therefore, a method involving oven curing was developed. Only one series of test were performed with this method due to lack of time but the method showed promising results.</p> / <p>Syftet med detta examensarbete var att undersöka möjligheten att använda en Dynamic Mechanic Thermal Analyzer (DMTA) för att mäta ökningen av styvhet som följd av filmbildning av latex i en torr bestrykning.</p><p>Två olika latexer användes för experimenten, en med Tg = 36°C (hård) och en med Tg = 8°C (mjuk). Den hårda latexen användes för att kunna göra tester på prover som ännu inte filmbildat när de torkat vid rumstemperatur och den mjuka latexen användes för att göra referens prover mot bestrykningen med hård latex.</p><p>Resultaten visade att det går att mäta styvhetsökning i bestrykningen som en följd av filmformation med DMTA och filmformation av latex i bestrykningen troligtvis beror på både tid, temperatur och provets historia. Ett försök att mäta vilken uppehålls tid vid en specifik temperatur som krävs för att filmbildningen skall fulländas genomfördes. Dessa försök visade att DMTA:n inte var en lämplig metod för att mäta denna tid då styvheten verkade öka under en längre tid. Detta kan bero på att pigment partiklarna packade sig tätare och på så sätt orsakade en ökning av styvheten. Därför gjordes ett annat försök som involverar ugns härdning, men på grund av tidsbrist blev det bara en mätserie utförd. Den sist nämnda metoden visade dock goda resultat och måste därför bedömas ha en potential.</p>

Polyetheretherketone (PEEK) is a designation given to materials of the polyaryletherketone family having a characteristic distribution of ether and ketone groups in the polymer backbone. PEEK materials have high strength and chemical resistance as well as very high melting points and glass transition temperatures. Because of this combination of properties, PEEK materials find use for wear application in extreme environments where they provide a light-weight and corrosion resistant bearing material that often does not require lubrication. An initial study focused on determining the effects of supplier and molecular weight on the wear of particular PEEK materials, in addition to the effect of contact pressure. This work is significant because it highlights the fact that tribologically relevant polymers, such as PEEK materials, vary greatly in terms of their polymer morphology and processing history, and this variation must be recognized by investigators when reporting wear data. Because of their light weight, chemical resistance, and self-lubricating properties, polymers are used in applications ranging from biomedical to aerospace. Some polymers exhibit significant differences in wear resistance based on whether they are in unidirectional or multidirectional sliding. Shear induced polymer chain orientation is believed to be responsible for this behavior. Polyetheretherketone (PEEK) has excellent wear resistance, but its multidirectional sliding behavior has not been thoroughly investigated. A factorial multidirectional pin-on-plate wear study of PEEK was conducted with a focus on molecular weight and sliding path directionality. These factors were studied for their correlation to overall wear performance. Additionally, transfer film thickness was measured at locations along the wear path using white light interferometry. A result of this work has been a greater understanding of PEEK wear mechanisms in various sliding configurations and how they relate to transfer film formation. A major outcome was the development of a quantitative metric to describe transfer film thickness and continuity. It was found that thinner more continuous transfer films form under sliding conditions that change direction rather than overlapping along the same path. The thinner more continuous transfer film was found to also correspond with statistically lower wear behavior. Scanning electron microscope (SEM) investigation of the transfer film and pin wear surface confirmed the relationship between transfer film quality and wear.

The objective of this master thesis was to investigate the possibility to measure the gain in stiffness of the dry coating due to film formation of latex with a Dynamic Mechanic Thermal Analyzer (DMTA). This could tell when and to which extent the latex forms a film after the drying process. Two latices with different Tg was used for the experiments, one with a Tg of 36°C, denoted hard, and the one with a Tg of 8°C, denoted soft. The hard latex was used to make coating samples that would not form a film when dried at room temperature and the soft latex was used as a reference to the coating with hard latex since it would form a film at room temperature. It was shown that a gain in stiffness due to film formation of latex in coating can be measured with a DMTA. It was also shown that that the film forming of latex in coatings depend on time, temperature and the history of the sample. Further investigations were carried out to try to determine the time for film formation to be completed at a certain temperature.. These investigations showed that this type of trials cannot be carried out in a DMTA directly since the stiffness seemed to increase monotonically during a very ling time. This might be due to the rearrangements in the pigment structure that might affect the gain in stiffness. Therefore, a method involving oven curing was developed. Only one series of test were performed with this method due to lack of time but the method showed promising results. / Syftet med detta examensarbete var att undersöka möjligheten att använda en Dynamic Mechanic Thermal Analyzer (DMTA) för att mäta ökningen av styvhet som följd av filmbildning av latex i en torr bestrykning. Två olika latexer användes för experimenten, en med Tg = 36°C (hård) och en med Tg = 8°C (mjuk). Den hårda latexen användes för att kunna göra tester på prover som ännu inte filmbildat när de torkat vid rumstemperatur och den mjuka latexen användes för att göra referens prover mot bestrykningen med hård latex. Resultaten visade att det går att mäta styvhetsökning i bestrykningen som en följd av filmformation med DMTA och filmformation av latex i bestrykningen troligtvis beror på både tid, temperatur och provets historia. Ett försök att mäta vilken uppehålls tid vid en specifik temperatur som krävs för att filmbildningen skall fulländas genomfördes. Dessa försök visade att DMTA:n inte var en lämplig metod för att mäta denna tid då styvheten verkade öka under en längre tid. Detta kan bero på att pigment partiklarna packade sig tätare och på så sätt orsakade en ökning av styvheten. Därför gjordes ett annat försök som involverar ugns härdning, men på grund av tidsbrist blev det bara en mätserie utförd. Den sist nämnda metoden visade dock goda resultat och måste därför bedömas ha en potential.

The dissertation thesis deals with the lubricant film formation chemistry on hip implant material surfaces with synovial fluid components. Biochemical and tribological properties of synovial fluid after joint replacement are focused, precisely on the chemical composition of the formed lubricating film and chemical structural changes of the associated constituents under mechanical loading. Nevertheless, the synovial fluid components‘ chemical structural changes after the joint replacement are rarely addressed and require further attention. Including metal and ceramics, various combination implant materials were applied within the lubricants of synovial fluid constituents separately and different model synovial fluids to reveal the biochemical reactions and frictional coefficients for understanding the possible lubrication mechanism. Raman Spectroscopic technique is manifested as the most appropriate method to explain the biochemical behaviour of synovial fluid and chemisorption on the surface of the implant material. The method is depicted presenting two different studies focusing on the chemical structure of the synovial fluid film on the implant surface and frictional coefficient measurement of the contact pair within the artificial hip joint. This latest methodological precedent also facilitates to evaluate the chemical structural change of the synovial fluid due to the tribological activity in the hip prosthesis. The thesis expounds original results concerning biotribology to increase the depth of knowledge on joint replacement procedure and to enhance the longevity of the orthopaedic implantations.

No description available.