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see document / Master of Engineering

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The overall goal of this work is to expand the materials library for the fused filament fabrication (FFF) material extrusion additive manufacturing (AM) process through innovations in the FFF process, post-process, and polymer composition. This research was conducted at two opposing ends of the FFF-processing temperature: low processing temperature (<100 °C) for pharmaceutical applications and high processing temperatures (>300 °C) for high-performance structural polymer applications. Both applications lie outside the typical range for FFF (190-260 °C). To achieve these goals, both the material and process were modified. Due to the low processing temperature requirements for pharmaceutical active ingredients, a water-soluble, low melting temperature material (sulfonated poly(ethylene glycol)) series was used to explore how different counterions affect FFF processing. The strong ionic interaction within poly(PEG8k-co-CaSIP) resulted in the best print quality due to the higher viscosity (105 Pa∙s) allowing the material to hold shape in the melt and the high-nucleation producing small spherulites mitigating the layer warping. Fillers were then explored to observe if an ionic filler would produce a similar effect. The ionic filler (calcium chloride) in poly(PEG8k-co-NaSIP) altered the crystallization kinetics, by increasing the nucleation density and viscosity, resulting in improved printability of the semi-crystalline polymer. A methodology for embedding liquids and powders into thin-walled capsules was developed for the incorporation of low-temperature active ingredients into water-soluble materials that uses a higher processing temperature than the actives are compatible with. By tuning the thickness of the printed walls, the time of internal liquid release was controlled during dissolution. This technique was used to enable the release of multiple liquids and powders at different times during dissolution. To enable the printing of high-temperature, high-performance polymers, an inverted desktop-scale heated chamber with the capability of reaching over 300 °C was developed for FFF. The design was integrated onto a FFF machine and was used to successfully print polyphenylsulfone which resulted in a 48% increase in tensile strength (at 200 °C) when compared to printing at room temperature. Finally, the effects of thermal processing conditions for printing ULTEM® 1010 were studied by independently varying the i) nozzle temperature, ii) environment temperature, and iii) post-processing conditions. The nozzle temperature primarily enables flow through the nozzle and needs to be set to at least 360 °C to prevent under extrusion. The environment temperature limits the part warping, as it approaches Tg (217 °C), and improves the layer bonding by decreasing the rate of cooling that allows more time for polymer chain entanglement. Post-processing for a longer time above Tg (18 hrs at 260 °C) promotes further entanglement, which increases the part strength (50% increase in yield strength); however, the part is susceptible to deformation. A post-processing technique was developed to preserve the parts' shape by packing solid parts into powdered salt. / Doctor of Philosophy / Fused filament fabrication (FFF) is the most widely used additive manufacturing (also referred to as 3D printing) process in industry, education, and for hobbyists. However, there is a limited number of materials available for FFF, which limits the potential of using FFF to solve engineering problems. This work focuses on material and machine modifications to enable FFF for use in both pharmaceutical and structural applications. Specifically, many pharmaceutical active ingredients require processing temperatures lower than what FFF typically uses. A low-temperature water-soluble material was altered by incorporating salt ions and ionic fillers separately. The differences in the printability were directly correlated to the measured variations in the viscosity and crystallization material properties. Alternatively, a technique is presented to embed liquids and powders into thin-walled, water-soluble printed parts that are processed using typical FFF temperatures, where the embedded material remains cool. The release time of the embedded material during dissolution is controlled by the thickness of the capsule structure. For structural applications, a machine was developed to allow for the processing of high-performance, high-temperature polymers on a desktop-scale system. This system uses an inverted heated chamber that uses natural convection to be able to heat the air around the part and not the electric components of the machine. The heated environment allows the part to remain at a higher temperature for a longer time, which enables a better bond between printed layers to achieve high-strength printed parts using high-performance materials. This machine was used to characterize the thermal processing effect for printing the high-performance polymer ULTEM® 1010. The nozzle temperature, environment temperature, and post-processing were tested where i) a higher nozzle temperature (360 °C) increases strength and prevents under extrusion, ii) a higher environment temperature (≥200 °C) increases the strength by slowing cooling and decreases warping by limiting the amount of shrinkage the occurs during printing, and iii) post-processing in powdered salt (18 hrs at 260 °C) increases part strength (50%) by allowing the printed roads to fuse.

Reliable sensing and monitoring systems based on optical fibers operating at high temperatures and in harsh environments are of high demand. One of the limitations of such systems is the devitrification of the fused silica based core and cladding glass at elevated temperatures. Crystallites can nucleate on the surface of the cladding and grow into the core. The formation of these crystalline flaws in the optical fiber causes stress concentration and extrinsic optical scattering and in addition leads to decreased mechanical properties and reduced optical stability. Commercial optical fibers of different compositions and core-cladding design were characterized in this study with respect to crystallization rate under various conditions. The optical stability was monitored with an optical spectrum analyzer. The crystallites were characterized with SEM and optical microscopy. The activation energies of crystallization for High OH and Low OH multimode fibers were estimated by measuring the crystal growth rate at different temperatures. The residual stress resulting from the formation of the crystals, which can lead to decreased mechanical performance of the fibers, was characterized with polarized light optical microscopy. The influence of water vapor in the atmosphere on the crystallization rate was determined. The features induced in the attenuation spectra were consistent with hydroxyl (OH) absorption peak. Spectral features such as thermal emission and hydroxyl absorption bands are discussed. The results obtained in this study can be used for selecting optical fibers for high temperature applications. / Master of Science / Reliable sensing and monitoring systems based on glass optical fibers operating at high temperatures and in harsh environments are in high demand. One of the limitations of such systems is the tendency of glass material to crystallize at elevated temperatures. Crystallites can nucleate on the surface of the fiber and grow inwards, impairing the optical and mechanical properties of the optical fiber. The formation of these crystalline flaws in the optical fiber can decrease the mechanical strength by causing stress concentrations and leading to formation of cracks, and reduce optical stability by causing light to scatter from the crystals. Commercial optical fibers of different compositions and geometry were characterized in this study with respect to crystal growth rate under various conditions, such as different temperatures (400-1350 °C), and different atmospheres (laboratory air and water vapor). The effect of crystals was demonstrated with respect to optical and mechanical performance. The results obtained in this study can be used for selecting optical fibers for high temperature applications.

Ceramic additive manufacturing is gaining popularity with methods like selective laser sintering (SLS), binder jetting, direct ink writing and stereolithography, despite their disadvantages. Laser sintering and binder jetting are too expensive, while direct ink writing lacks resolution and stereolithography lacks scalability. The project aims to combine one of the most versatile, affordable, and readily available 3D printing methods: fused filament fabrication (FFF) with polymer derived ceramics to produce cellular ceramics to overcome the disadvantages posed by the other methods. The process uses a two-step approach. The first step is to 3D print the part using a polymer FFF 3D printer with a thermoplastic polyurethane filament and the second step is to impregnate the part in a polysilazane preceramic polymer and then pyrolyze it in an inert environment up to 1200C. The resulting product is a high-resolution cellular ceramic of the composition SiOC(N). This type of cellular ceramic can find an application in several fields such as scaffolds for bone tissue regeneration, liquid metal filtering, chemical and gas filtering, catalytic converters and electric applications. The process can provide an affordable alternative to the products used in these fields currently.

The aim of this thesis was to examine materials using high resolution X-ray diffraction techniques. Initial work involved the synthesis of various metal phosphates to investigate their suitability for charge density work. Many of these were discovered to be of insufficient quality for further study. Much of the phosphate synthesis work performed at the moment utilises an ionic liquid both as a solvent and structure directing agent which dictates the topology of the structure due to its size and charge density. As such the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate used in the synthesis process was examined with high resolution X-ray diffraction as it was possible to produce large pure crystals which could be examined further. A high resolution data set was also collected from the metal organic framework SIMOF-1 which produced a preliminary multipole model however further data collections are required to improve the quality of the model. A multi-technique investigation involving X-ray diffraction, solid state NMR and first principles calculations was carried out on the aluminophosphate material AlPO₄-15. A synchrotron X-ray single crystal diffraction study was carried out on the same sample as that used in solid state NMR studies. The model from the single crystal study, together with a model from a literature high resolution study of the same material, were used as starting points for the first-principles calculations of the NMR parameters. This enabled the ³¹P and ²⁷Al NMR spectra to be unambiguously assigned and all the NMR parameters calculated agreed well with the experimental spectra even without relaxing the X-ray derived structural models. Highlighting that as long as a good data set has been collected in the first place the atomic positions would not change too drastically. Other aspects of this thesis involved investigations into other ionothermally prepared systems such as the use of different phosphonate sources to provide functionality to the materials. This work resulted in some interesting findings such as the ionic liquid breaking down and being incorporated into the framework via the metal. Many of the structures produced were of a layered nature however a molecular structure was also synthesised which is unlike the vast majority of hydrothermally prepared phosphonates, which are layered. The negligible vapour pressure provided by the ionic liquid has enabled synthesis reactions to be investigated with glass vessels on an energy dispersive beam line. This work highlighted how it is possible to study the synthesis process in-situ and compare microwave assisted reactions against a conventional heating method, the results indicate that two different types of reactions are occurring resulting in different intermediates which is due to the way the reagents are heated. The microwave assisted reactions also result in larger purer crystals which highlights the importance of the method in materials synthesis. The use of a specially designed environmental gas cell was used to investigate the adsorption properties of the metal organic framework CPO-27-Co in-situ. Using the cell it was possible to locate sulfur dioxide physisorbed and chemisorbed sites with in the framework which could be removed by the application of a vacuum and heat. It was also possible to locate the chemisorbed sites for nitric oxide within the metal organic framework however due to the low scattering factor and disorder from the gas it was not possible to locate the physisorbed sites.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The specific goal of the investigation was the measurement, as a function of temperature, of the self-diffusion coefficients of Pb210 and Cl36 in PbCl2-KCl compositions in the region of the first compound, and to calculate from these data the activation energy necessary for the diffusion of these ions.