The goal of this thesis was to design thermally responsive polyol resins that would be compatible with isocyanates. Two approaches were made to reach this goal, the first involved functionalizing soybean oil and the second involved post-polymerization modification of a methacrylate based resin. A soybean based coating with thermally responsive Diels-Alder linkages has been prepared following an automotive two-component formulation. The resulting coatings displayed the capability to be healed following physical deformation by a thermal stimulus, and such a material has significant potential for end users. Various curing agents were employed, and resulted in variation of scratch resistance and re-healablity. Different thermally responsive soybean resins were synthesized to have varying amounts of reversible and nonreversible linkages when incorporated into the coating. Additionally, different isocyanates were added at differing ratios of NCO:OH in search of the optimum coating. It was found through the analysis of re-healabilty, hardness, gloss, and adhesion that the optimal combination was an acetylated resin (no irreversible crosslinks) with 54% reversible Diels Alder linkages at an NCO:OH ratio of 5:1 using isophorone diiscocyanate. Materials were evaluated via differential scanning calorimetry (DSC), scratch resistance, Koenig hardness, gloss measurements, and topographical analysis. In the second project, copolymerization of methyl methacrylate and 2-isocyanatoethyl methacrylate via free radical polymerization was done to synthesize a polymer with pendant isocyanates. The isocyanate was used as a chemical handle to incorporate Diels-Alder linkages into the PMMA resin. The PMMA resin with Diels-Alder linkages was successfully synthesized and incorporated into a polyurethane gel as proven via 1H NMR and IR. The gel showed thermal reversibility at 120°C due to retro-DA reaction via DSC as well as thermally reversible bulk properties.

Ever since the advent of polymer science, polyurethanes have played a huge role in the industrial world. They have been used in endless applications from furniture padding to aircraft coatings, to binders for insensitive munitions. It is therefore important that the chemistry of polyurethanes is well understood as well as the ability to draw relationships between the raw materials selected and the end-use properties of the polymer. Because of the multitude of practical applications, the development of an undergraduate polymer chemistry laboratory focused on polyurethane elastomers is developed and described herein. Polymer chemistry students are exposed to hydroxyterminated polybutadiene (HTPB) polyols as well as di- and multifunctional isocyanates for use in a tin-catalyzed reaction. The effect of catalyst concentration and crosslinking agent on cure time, prepolymer structure on end-use properties, and the effect of crosslink density on physical properties are explored. Students also receive a very important introduction to statistical experimental design. They learn when using statistical experimental design is necessary, and they learn how to manipulate, analyze, and interpret data using two-way ANOVA in Minitab. The development of the lab experiment also led to extrapolating the use of polyurethane elastomers into a new application, the development of a polyurethane spinal muscular atrophy (SMA) brace. SMA is a neurodegenerative disorder that results in the mutation or deletion of the spinal motor neuron gene, resulting in the atrophy of a subject’s spine muscles throughout the continuation of their life. These patients are therefore forced to wear a brace for the entirety of their lives. The current brace technology in use by SMA patients is limited by the fact that SMA affects a very small amount of the population and therefore it is not cost-effective for industry to develop a brace technology designed for these patients. Scoliosis braces such as thoracolumbrosacral orthoses (TLSOs) are too hard and too uncomfortable for patients with SMA; therefore, the polyurethane elastomer was extrapolated to develop a brace with more flexibility and more durability. Two generations of polyurethane elastomeric brace were developed and evaluated by a subject and family with an SMA background. The brace is a much improved technology to the TLSO braces and provides more flexibility, more mobility, greater comfort, and superior modularity to the old technology. An instruction manual is also included with a step-by-step process of how to reproduce the brace.

<p dir="ltr">There is a plethora of applications that require chemical patterning on the molecular scale. While the surface science community has made tremendous progress in achieving this level of control on hard, crystalline interfaces, significant challenges are associated with extending this progress to less “perfect” systems such as soft, amorphous interfaces. Applications ranging from soft robotics and wearable electronics to regenerative medicine often utilize polymeric materials such as polydimethylsiloxane (PDMS) and hydrogels. These materials have advantageous properties, including biocompatibility and mechanical tunability. Biological applications, for example, often require the display of functional groups with precise spatial resolution. Cellular behavior is dictated by biochemical and biophysical cues in the extracellular matrix; therefore, substrate properties, including stiffness and ligand density, must be independently tunable. Soft, polymeric materials are highly heterogenous with pore sizes ranging from 10 nm to 1 µm and hence, particularly difficult to pattern below the length scale of substrate heterogeneity. Furthermore, deconvolving mechanical properties such as elastic modulus from the density of surface-active functional groups is especially challenging, with softer materials typically corresponding is lower ligand densities. Additionally, many traditional surface science characterization and patterning methods are incompatible with soft interfaces (e.g. amorphous surface structure, low mechanical strength, hydrated environment). Recently, we have reported a method capable of achieving high-resolution chemical patterning of PDMS and hydrogels. Long studied within the scanning probe community, amphiphiles with long alkyl chains self-assemble into lying down stripe phases on highly ordered pyrolytic graphite (HOPG), generating 1-nm-wide stripes of functional headgroups between 5-nmwide stripes of exposed alkyl chains. Stripe phases of functional diacetylenes (DA) are photopolymerized, producing a polydiacetylene backbone that tethers together adjacent molecules, generating a PDA film on HOPG (sPDA). We have shown that PDA films on HOPG can be transferred to PDMS as well as polyacrylamide hydrogels. When PDMS is cured in contact with sPDAs, the PDA backbones can act as a site for hydrosilylation, the same reaction responsible for PDMS curing, covalently linking sPDAs to the PDMS mesh. Careful exfoliation reveals nm-scale functional patterns on the surface layer of PDMS. 10 Here, we examine the impact of PDMS structural components on the efficiency of interfacial reactions between sPDAs and the PDMS network. We also illustrate the impact of PDAfunctionalized PDMS on the adhesion and spreading behavior of C2C12 murine myoblasts.</p>

The fact that characteristic crystalline products result upon the diffusion of arsenate ions into silicic acid gel which has been impregnated with stannous ions has been known by the Pacific Chemistry Department for some time. The optimum conditions with regards to heat and hydrogen ion concentration have been determined. The purpose of this investigation was to study the products of the reaction. First to determine whether or not the silicic acid itself combined with the stannous and arsenate. ions in the formation of the crystalline product, and second to determine its chemical composition.

This research thesis covers work done on building an atomic layer deposition (ALD) reactor followed by the development and optimization of an ALD process for indium oxide thin films on crystalline silicon substrates from new precursors using this new homebuilt cost-effective tool. This work describes the design, building and testing of the ALD system using an indium triazenide precursor and water in a novel precursor combination. The reactor was built to be capable of depositing films with comparable results to commercially built systems.Indium oxide thin films were deposited as the deposition temperature was varied from 154 to 517 0C to study the effects of deposition temperature on the obtained film thicknesses and ascertain the ALD temperature window between 269-384 0C. The presence of indium oxide films was confirmed with X-ray diffraction analysis, which was also used to study their crystallinity. The films were found to have a polycrystalline structure with a cubic phase. Measurement of film thickness was performed using X-ray reflectivity which determined a growth rate of approximately 1 Å/cycle. Elemental composition was determined by X-ray photoelectron spectroscopy which confirmed contamination-free indium rich films. Scanning electron microscope imaging was used to examine the surface morphology of the films as well as thick cross-sectional thicknesses.Since indium oxide films are potentially useful in various electronic, optical, and catalytic applications, emphasis is also placed on the accurate characterization of the chemical and physical properties of the obtained thin films. Optical and electrical properties of the produced transparent conducting oxide films were measured for transparency (and optical band gap) and electrical characterization by resistivity measurements, from UV-Vis spectrophotometry and 4-point probe data respectively. A high optical transmission &gt;70 %, a wide band gap 3.99-4.24 eV, and low resistivity values ∼0.2 mΩcm, showed that In2O3 films have interesting properties for various applications confirming indium oxide a key material in transparent electronics.

This master thesis was a part of an ongoing project at Research institutes of Sweden (RISE) and Chalmers University of technology, studying the formation of white layers (WLs) upon hard machining AISI 52100 steel. With a focus on the nanocrystalline microstructure of the machined steel, X-ray diffraction (XRD), white light interferometry (WLI), optical microscopy (LOM) and scanning electron microscopy (SEM) was utilized in the analysis of gathering an in-depth understanding of the WL formation mechanism. By introducing varying cutting parameters as part of the machining process, the effect of cutting speed and tool wear could be observed to directly impact the WL formation and could be linked to the thermomechanical contribution to the formation mechanism. Both thermal and mechanical WLs were observed and could be distinguished by the occurrence of dark layers in thermal WLs. The purpose of this thesis was to observe the influence of retained austenite (RA) on WL formation and from the XRD analysis the residual stress for different RA content could not be concluded. Furthermore, SEM concluded differences in the microstructure where a higher abundance of carbides was observed in the case of lower RA, a phenomenon most likely originating in the heat treatment process. Indications of facilitated mechanical WL formation for lower RA was observed but could not be deemed conclusive. The RA content could not be concluded to have an impact on the surface roughness nor the residual stress where variations were rather linked to the cutting parameters.

There is a constant search for new sustainable materials. A material that has become increasingly more interesting is cellulose, since it is both renewable and biodegradable. By combining cellulose nanofibrils (CNF) and the polymer complex poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), a conductive hydrogel can be made. The hydrogel can subsequently be used to 3D-print various structures, which further can be used in multiple applications such as microrobots, sensors and smart devices. The aim of this bachelor thesis was to develop a 3D-printable hydrogel composed of PEDOT:PSS and CNF was made. The goal was to print and crosslink a conductive structure, and subsequently induce electrical current through the structure to facilitate movement (i.e. artificial muscles). Several hydrogel inks composed of CNF and PEDOT:PSS were prepared across a range of concentrations. Homogenisation of the hydrogels was achieved through various mixing techniques. Both freeze-drying and evaporation were tested to concentrate the hydrogels. Furthermore, crosslinking tests were performed using iron(III)chloride hexahydrate and citric acid, followed by a conductivity measurement. Lastly, rheology tests were performed on four of the inks. The optimal concentration of solid material was determined to be 4.8 wt% and the most favourable way of concentrating the hydrogels was by freeze drying. Furthermore, iron(III)chloride hexahydrate was found to be more favourable when crosslinking the hydrogels. The conductivity measurements showed that crosslinking with iron(III)chloride hexahydrate resulted in a notable increase in conductivity in the material. Lastly, the rheology measurements showed that the 4.8 wt% hydrogel ink had high elasticity, viscosity and exhibited shear thinning behaviour. / Det söks konstant efter nya hållbara material. Ett material som har blivit alltmer intressant är cellulosa, eftersom det både är förnybart och bionedbrytbart. Genom att kombinera cellulosa nanofibriller (CNF) och polymer komplexet poly(3,4-etylendioxitiofen) polystyrensulfonat (PEDOT:PSS), kan en konduktiv hydrogel framställas. Denna hydrogel kan sedan användas för att 3D-printa en mängd olika strukturer, vilka senare kan används i olika tillämpningar så som mikrorobotar, sensorer och smarta enheter. Målet med detta kandidatarbete var att utveckla en hydrogel av PEDOT:PSS och CNF för användning i 3D-skrivare. Målet var att printa och korslänka en struktur med konduktiva egenskaper, vilken senare skulle induceras med elektricitet för att främja rörelse, med andra ord artificiella muskler. Ett flertal hydrogeler av CNF och PEDOT:PSS förbereddes i en rad olika koncentrationer. Homogenisering av hydrogelerna uppnåddes genom att testa olika metoder för omrörning. Både frystorkning och avdunstning testades för att koncentrera hydrogelerna. Dessutom undersöktes tvärbindning genom järn(III)kloridhexahydrat och citronsyra, följt av en konduktivitetsmätning. Slutligen utfördes reologimätningar på fyra av de framställda hydrogelerna. Den optimala koncentrationen av fast material i en hydrogel bestämdes till 4,8 vikt% och det mest gynnsamma sättet att koncentrera hydrogeler var genom frystorkning. Vidare, var järn(III)kloridhexahydrat ett mer fördelaktigt alternativ vad gällde tvärbindning av hydrogelerna. Konduktivitetsmätningarna visade att tvärbindning med hjälp av järn(III)kloridhexahydrat ökade konduktiviteten märkbart hos materialet. Slutligen visade reologimätningarna att hydrogelen med 4,8 vikt% hade hög elasticitet, viskositet och den uppvisade även skjuvningstunnande beteende.

<p>This thesis evaluates several solid-state NMR spectroscopy approaches to studying lithium ion dynamics in solid-state electrolytes. With the goal of reducing the risks associated with current liquid electrolytes, solid-state electrolytes provide non-flammable materials that are also stable against attack by cathode and anode materials. Solid-state NMR spectroscopy offers a versatile method to determine structural details and can also provide information about ion mobility in solid-state electrolytes. Challenges involved in the study of solid-state electrolytes include the difficulty in distinguishing between ^6,7Li resonances due to the small chemical shift range of diamagnetic lithium species. The NMR methods selected in this thesis aim to circumvent some of these issues in order to determine structural and dynamic properties in solid-state electrolytes. Several different electrolytes have been examined including LaLi_0.5Fe_0.2O_2.09 and related materials, which exhibit intricate structural properties. ¹³⁹La NMR spectroscopy, in combination with ⁷Li MAS NMR spectroscopy, was used to determine the nature of this disorder. In addition, studies of the quadrupolar framework ⁸⁷Rb nucleus, which take advantage of its large electric field gradient, have been used to indirectly probe the activation energy for Ag⁺ ion hopping in the solid-state silver ion electrolyte RbAg₄I₅. Alternatively, dipolar coupling between ⁶Li and ⁷Li has been used to compare lithium ion hopping rates in Li₆BaLa₂M₂O₁₂ (M = Ta, Nb) using ⁶Li{⁷Li}-REDOR NMR studies. Finally, T₂ relaxation studies have been used to probe ion dynamics in Li₃V₂(PO₄)₃ and LiVO₃ in order to determine if this is a viable method to study dynamics in these materials.</p> / Doctor of Philosophy (PhD)

This study focuses on the visible light response of hetero-structures of TiO2-graphene- MoS2 for solar energy harvestings. The commercial P25 TiO2 nano-particles, and selfprepared layered reduced graphene oxides (RG) and MoS2 were assembled for the targeted hetero-structure materials as visible-light responsible solar harvesting cocatalysts. The hydrothermal method was applied for nano-material synthesis, the reduction of graphene oxides, and bonding formation. Multiple characterization methods (SEM-TEM, XRD, XPS, UV-VIS, PL, FT-IR, TGA) have been applied to understand the electron-hole pair separation and recombination, and performance tuning in their visible-light photo-catalysis rhodamine B (Rh.B) degradations process Compared to TiO2, an obvious red shift of light absorption (from 3.1 eV to 2.6 eV) of the as-prepared RG-TiO2 was observed by UV-vis analysis, and an enhanced photocatalytic degradation of the Rhodamine B (Rh.B) using the as-prepared RG-TiO2 was also observed in a Xe lamp exposure test. The explication of these two approaches to photocatalytic improvements were concluded as the energy gap changing, the formation of Ti-O-C chemical bonds between TiO2 and RG for charge transfer and the reduction of the band gap, as well as a likelihood of up-conversion photoluminescence mechanism (UCPL). The synthesis temperature was found to be critical factor to control binding formation and agglomeration of nano-materials. The lower and higher temperatures induced ineffective formations of preferable bonding structures and the significant agglomeration. The optimal synthesis temperature was found to be within 120 ℃-150 ℃ in the TiO2-RG system. For better understanding of the Ti-O-C bonding, a heterostructure of TiO2 nanotube arrays with GO (TNA-GO) was synthesized using the Langmuir-Blodgett (LB) assembly method. The band gap of this assemble was very close to the previous TiO2-RG synthesized below 120 ℃, which is very close to that of TiO2 nano-particles. This lead to the conclusion on the significance of the Ti-O-C bonding in the visible-light-responsible photo-catalysis solar harvestings. This study revealed the fundamental mechanisms on the bonding formations and the significant visible-light-response of hetero-structcures between commercial-available, inexpensive and non-toxic TiO2 and layered materials, such as the zero-band-gap graphene and the smaller-band-gap MoS2. This mechanisms understanding will greatly sustain applications of economical-effective and environmental-safe TiO2.

Transmission electron microscopy (TEM) is a powerful tool for studying solidstate crystalline systems. With the advances in aberration correction, monochromation, and in situ capabilities, these microscopes are now more useful for addressing fundamental materials chemistry problems than ever before. This dissertation will illustrate the ways in which I have been using high-resolution imaging and in situ heating in the TEM during my Ph.D. research to investigate unique solid state chemistry questions. This dissertation will focus on four unique crystal systems: thermoelectric skutterudite crystals, vapor-liquid-solid (VLS) grown nanowires, and hafnium dioxide nanorods. Although these systems are very different from one another, high resolution and/or in situ heating in TEM is an integral part of each study. Through these techniques, we gain insight and knowledge of these systems that may have gone unknown through different analysis techniques. The experiments I will describe in some cases provide surprising and unexpected results that arise from the nanoscale nature of the materials and would be difficult to observe through bulk analytical methods. The work presented here helps to demonstrate the strength and versatility of TEM to address solid state chemistry questions.