<p>Fabricating complex submicron 3D structures can be achieved by multi-photon lithography, especially two-photon lithography is commonly used to obtain precision and flexibility in printing sophisticated sub-micron 3D structures. Several disadvantages stemmed from a two-photon lithography experiment setup, including cost, the necessity of a large laboratory space to use a femtosecond laser and a high-order process. A two-step absorption is chosen instead of two-photon lithography as a primary excitation process achieving the same degree of quadratic optical non- linearity as two-photon lithography at a lower cost with a relatively compact laboratory size. The working mechanism of Two-step absorption is the following. Quadratic nonlinearity comes from radicals from excited triplet states photoinitiators. Ground states of photoinitiators get excited by the incident laser. Those excited singlet photoinitiators go through the intersystem crossing, becoming the ground triplet state of photoinitiators. There are two branches after the ground triplet states, especially for photoinitiator benzil molecules with the incident laser on. Either it becomes a radical without photons received from the incident laser or gets excited again to an excited triplet state by the incident laser. Those excited triplet-state photoinitiator molecules become radicals that occur in polymerization. However, those from the ground triplet states add linearity to polymerization. When it comes to multiple exposures, the linearity becomes problematic, especially outside the region and tails of the voxel. For example, suppose the intensity at two tails of the voxel is 1% relative to the maximum intensity at the focal point. In that case, the absorbed dose will be added up to the maximum intensity at the focal point when it comes to 100 exposures. Quadratic nonlinearity and linearity are jumbled together in the current two-step absorption process. In this work, optimization of photoinitiator concentration was conducted to reduce the linearity. Confined and high throughput 3D structure fabrications are achieved by controlling initiator depletion. Simulations are also developed with multi-physics models to compare with the empirical results.</p>

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Additively manufactured parts produced using selective laser melting (SLM) are prone to defects created during the build process due to part shrinkage while cooling. Currently defects are found only after the part is removed from the printer. To determine whether cracks can be detected before a print is completed, this project developed print parameters to print a test coupon with inherent defects – warpage and cracking. Data recorded during the build was then characterized to determine when the defects occurred. The test coupon was printed using two sets of print parameters developed to control the severity of warpage and cracking. The builds were monitored using an accelerometer recording at 12500 samples per second, an iphone recording audio at 48000 samples a second, and a camera taking a photo every build layer. Data was analyzed using image comparison, signal amplitude, Fourier Transform, and Wavelet Decomposition. The developed print parameters reduced warpage in the part by better distributing heat throughout the build envelope. Reducing warpage enabled the lower portion of the part to be printed intact, preserving it to experience cracking later in the build. From physical evidence on the part as well as time stamps from the machine script, several high energy impulse events in the accelerometer data were determined to be when cracking occurred in the build. This project’s preliminary investigation of accelerometers to detect defects in selective laser melting will be used in future work to create machine learning algorithms that would control the machine in real time and address defects as they arise.

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Projektet syftar till att föreslå en rimlig riktning för hur additiva produktionsmetoder, alltså tillverkningsmetoder som använder lager-på-lager-teknik, kan tänkas påverka arkitekturen, att försöka sätta sig in i teknikerna och komma fram till vilken riktning som upplevs mest givande eller gångbar. Hur ska man nyttja potentialen med den nya tekniken på ett bra sätt? Jag har försökt ta fram en produkt som nyttjar potentialen hos de additiva produktionsmetoderna och som upplevs tänkbar för fullskalig realisering i byggsektorn i en närliggande framtid. Produkten består av en metod för framställning av en sandwichkonstruktion med hög trähalt och troligen lång livslängd. Metoden minskar byggsektorns klimatbelastning och kan ge stora rumsliga kvaliteter och formgivningsmöjligheter. Jag har genom fysiska experiment och utforskande av olika digitala fabrikationsmetoder försökt att visualisera och identifiera möjligheter med dessa nya tekniska hjälpmedel. Genom praktiska tester har jag prövat mina föreställningar av hur dessa metoder kan användas på effektiva sätt. Projektet vidga-des från att initialt omfatta additiva produktionsmetoder till att senare under tillämpningsfasen även omfatta digitala hjälpmedel såsom fotogrammetri och verktyg för parametrisk design. Projektet har resulterat i ett tillvägagångsätt för printning av cellulosabaserade sandwichkonstruktioner i printade formverk av återvinningsbar biokomposit. / The project aims to propose a direction for how additive manufacturing methods can influence architecture, to study the techniques and find out which direction could be perceived as most rewarding or viable. How to use the potential of the new technology in a good way? I have tried to develop a product that utilizes the potential of the additive manufacturing methods and which is conceivable for full-scale realization in the construction sector in the near future. The product consists of a method for producing long lasting sandwich constructions with high wood content. The method reduces the building industry's climate impact and can provide great spatial qualities and design possibilities. Through physical experiments and exploration of various digital fabrication methods, I have tried to visualize and identify possibilities with these new technological aids. Through practical tests, I have tested my ideas of how these methods can be used effectively. The project was expanded from initially studying additive production methods to, later during the application phase, also include digital aids such as photogrammetry and tools for parametric design. The project has resulted in a strategy for printing cellulose-based sandwich constructions in printed molds of recyclable biocomposite.

The growing popularity of additive manufacturing in commercial applications has al- lowed for new ideas and new ways of thinking when designing components. Further optimization at the component level is possible, though powder metallurgy is in its infancy. This study explores the possibility of using additive manufacturing to develop better labyrinth seals in turbomachinery. Labyrinth seals have a torturous fluid path with high losses, thus limiting the amount of fluid leakage. These types of seals can be non-rotating, allowing them to better take advantage of the additive manufacturing process due to the absence of rotating stresses. Labyrinth seal performance is defined by its ability to limit leakage through a seal. Investigations on the ability to reduce this leakage using the inherent roughness from the additive manufacturing process and the addition of complex geometry only capable of being produced by additive manufacturing are explored. Incompressible and compressible fluid models are utilized in the study. Perfectly smooth seals with tooth counts of four, six, and eight are first simulated using ANSYS FLUENT and compared to theoretical models to determine accuracy. Roughness is then applied to the seals and leakage decreases of 0.5% to 1.5% are experienced for the incompressible model. Decreases of 1.0% to 3.5% are experienced for the compressible model. Flow visualization and line analysis are conducted for all seals tested to understand how fluid flow is behaving within the clearance region of the seal and seal chambers. Several additive manufacturing geometries are simulated against a control seal to determine geometries with the largest effect on leakage rates. These geometries are then adapted to a six tooth seal and simulated with roughness. This additively manufactured seal is then compared to the smooth and rough six tooth seal for both incompressible and compressible fluids. Leakage was decreased by 5% to 8% for the incompressible model and 5% to 7% reductions for the compressible model when compared to the smooth seal. Flow visualization and line analysis were also conducted for the additively manufactured six tooth seal. A basic outline for an experiment and test stand were developed for future work.

Processing of ceramics has always been difficult due to how hard and brittle the material is. Fused Deposition of Ceramics (FDC) is a method of additive manufacturing which allows ceramic parts to be built layer by layer, abetting more complex geometries and avoiding the potential to fracture seen with processes such as grinding and milling. In the process of FDC, a polymeric binder system is mixed with ceramic powder for the printing of the part and then burned out to leave a fully ceramic part. This experiment investigates a new combination of materials, zirconia and acrylic binder, optimizing the process of making the material into a filament conducive to the printer system and then performing trials with the filament in the printer to assess its feasibility. Statistical analysis was used to determine optimal parameter levels using response surface methodology to pinpoint the material composition and temperature yielding the highest quality filament. It was discovered that although the mixture had adequate melting characteristics to be liquefied and printed into a part, the binder system did not provide the stiffness required to act as a piston to be fed through the printer head. Further studies should be completed continuing the investigation of zirconia and acrylic binder, but with added components to increase strength and rigidity of the filament.

Additive manufacturing is a growing field dominated by printing processes that soften and re-solidify material, depositing this material layer by layer to form the printed shape. Increasingly, researchers are pursuing new materials to enable fabrication of a wider variety of associated capabilities. This includes fabrication with high-viscosity materials of many new classes of material compositions, such as doping for magnetic or electrically conducting polymers. These additives complicate the materials deposition process by requiring complex, non-linear calibration to synchronize these new candidate materials with the additive manufacturing software and hardware. In essence, additive manufacturing is highly dependent on identifying the delicate balance between materials properties, hardware, and software-which is currently realized via a time-consuming and costly iterative calibration process. This thesis is concerned with reducing this cost of calibration, in particular by providing a time-based metric based on material viscosity for material retraction at the conclusion of each extrusion. It presents a novel non-contact method of determining the material retraction rate (during reversal of extrusion), by measuring the variation in laser intensity resulting from the deformation of the material reservoir due to change in material pressure. Commercially available laser measurement systems cost more than $20,000 and are limited to 1 μm at a 300 ms (3 Hz) sampling rate. The experimental setup presented in this thesis costs less than $100 and is capable of taking measurements of 1 - 2 μm at a 0.535 ms (1870 Hz) sampling rate. For comparison, the stepper motor driving the material extruder operates at 0.667 ms (1500 Hz). Using this experimental setup, an inverse correlation is shown to exist between the viscosity of a material and the rate at which the material is retracted. Using this correlation and a simplified material analysis process, one can approximate the retraction time necessary to calibrate new materials, thereby significantly improving initial estimated calibration settings, and thus reducing the number of calibration iterations required to ready a new material for additive manufacturing. In addition, the insight provided into the material response can also be used as the basis for future research into minimizing the calibration process. / Master of Science

Additive manufacturing (AM) fabricates complex geometries inaccessible through other manufacturing techniques. However, each AM platform imposes unique process-induced constraints which are not addressed by traditional polymeric materials. Vat photopolymerization (VP) represents a leading AM platform which yields high geometric resolution, surface finish, and isotropic mechanical properties. However, this process requires low viscosity (<20 Pa·s) photocurable liquids, which generally restricts the molecular weight of suitable VP precursors. This obstacle, in concert with the inability to polymerize high molecular weight polymers in the printer vat, effectively limits the molecular weight of linear network strands between crosslink points (Mc) and diminishes the mechanical and elastic performance of VP printed objects. Polymer colloids (latex) effectively decouple the relationship between viscosity and molecular weight by sequestering large polymer chains within discrete, non-continuous particles dispersed in water, thereby mitigating long-range entanglements throughout the colloid. Incorporation of photocrosslinking chemistry into the continuous, aqueous phase of latex combined photocurability with the rheological advantages of latex and yielded a high molecular weight precursor suitable for VP. Continuous-phase photocrosslinking generated a hydrogel scaffold network which surrounded the particles and yielded a solid "green body" structure. Photorheology elucidated rapid photocuring behavior and tunable green body storage moduli based on scaffold composition. Subsequent water removal and annealing promoted particle coalescence by penetration through the scaffold, demonstrating a novel approach to semiinterpenetrating network (sIPN) formation. The sIPN's retained the geometric shape of the photocured green body yet exhibited mechanical properties dominated by the high molecular weight latex polymer. Dynamic mechanical analysis (DMA) revealed shifting of the latex polymer and photocrosslinked scaffold T_g's to a common value, a well-established phenomenon due phasemixing in (s)IPN's. Tensile analysis confirmed elastic behavior and ultimate strains above 500% for printed styrene-butadiene rubber (SBR) latexes which confirmed the efficacy of this approach to print high performance elastomers. Further investigations probed the versatility of this approach to other polymer compositions and a broader range of latex thermal properties. Semibatch emulsion polymerization generated a systematic series of random copolymer latexes with varied compositional ratios of hexyl methacrylate (HMA) and methyl methacrylate (MMA), and thus established a platform for investigating the effect of latex particle thermal properties on this newly discovered latex photoprocessing approach. Incorporation of scaffold monomer, N-vinyl pyrrolidone (NVP), and crosslinker, N,N'-methylene bisacrylamide (MBAm), into the continuous, aqueous phase of each latex afforded tunable photocurability. Photorheology revealed higher storage moduli for green bodies embedded with glassy latex particles, suggesting a reinforcing effect. Post-cure processing elucidated the necessity to anneal the green bodies above the T_g of the polymer particles to promote flow and particle coalescence, which was evidenced by an optical transition from opaque to transparent upon loss of the light-scattering particle domains. Differential scanning calorimetry (DSC) provided a comparison of the thermal properties of each neat latex polymer with the corresponding sIPN. Another direction investigated the modularity of this approach to 3D print mixtures of dissimilar particles (hybrid colloids). Polymer-inorganic hybrid colloids containing SBR and silica nanoparticles provided a highly tunable route to printing elastomeric nanocomposite sIPN's. The bimodal particle size distribution introduced by the mixture of SBR (150 nm) and silica (12 nm) nanoparticles enabled tuning of colloid behavior to introduce yield-stress behavior at high particle concentrations. High-silica hybrid colloids therefore exhibited both a shear-induced reversible liquid-solid transition (indicated by a modulus crossover) and irreversible photocrosslinking, which established a unique processing window for UV-assisted direct ink write (UV-DIW) AM. Concentric cylinder rheology probed the yield-stress behavior of hybrid colloids at high particle concentrations which facilitated both the extrusion of these materials through the UV-DIW nozzle and the retention of their as-deposited shaped during printing. Photorheology confirmed rapid photocuring of all hybrid colloids to yield increased moduli capable of supporting subsequent layers. Scanning electron microscopy (SEM) confirmed well-dispersed silica aggregates in the nanocomposite sIPN's. DMA and tensile confirmed significant reinforcement of (thermo)mechanical properties as a result of silica incorporation. sIPN's with relative weight ratio of 30:70 silica:SBR achieved maximum strains above 300% and maximum strengths over 10 MPa. In a different approach to enhancing VP part mechanical properties, thiol-ene chemistry provided simultaneous linear chain extension and crosslinking in oligomeric diacrylate systems, providing tunable increases to Mc of the photocured networks. Hydrogenated polybutadiene diacrylate (HPBDA) oligomers provided the first example of hydrocarbon elastomer photopolymers for VP. 1,6-hexanedithiol provided a miscible dithiol chain extender which introduced linear thiol-ene chain extension to compete with acrylate crosslinking. DMA and tensile confirmed a decrease in T_g and increased strain-at-break with decreased crosslink density. Other work investigated the synthesis and characterization of first-ever phosphonium polyzwitterions. Free radical polymerization synthesized air-stable triarylphosphine-containing polymers and random copolymers from the monomer 4-(diphenylphosphino) styrene (DPPS). ³¹P NMR spectroscopy confirmed quantitative post-polymerization alkylation of pendant triarylphosphines to yield phosphonium ionomers and polyzwitterions. Systematic comparison of neutral, ionomer, and polyzwitterions elucidated significant (thermo)mechanical reinforcement by interactions between large phosphonium sulfobetaine dipoles. Broadband dielectric spectroscopy (BDS) confirmed the presence of these dipoles through significant increases in static dielectric content. Small-angle X-ray scattering (SAX) illustrated ionic domain formation for all charged polymers. / Doctor of Philosophy / Additive manufacturing (AM) revolutionizes the fabrication of complex geometries, however the utility of these 3D objects for real world applications remains hindered by characteristically poor mechanical properties. As a primary example, many AM process restrict the maximum viscosity of suitable materials which limits their molecular weight and mechanical properties. This dissertation encompasses the design of new photopolymers to circumvent this restriction and enhance the mechanical performance of printed materials, with an emphasis on elastomers. Primarily, my work investigated the use of latex polymer colloids, polymer particles dispersed in water, as a novel route to provide high molecular weight polymers necessary for elastic properties in a low viscosity, liquid form. The addition of photoreactive molecules into the aqueous phase of latex introduces the necessary photocurability for vat photopolymerization (VP) AM. Photocuring in the printer fabricates a three-dimensional object which comprises a hydrogel embedded with polymer particles. Upon drying, these particles coalesce by penetrating through the hydrogel scaffold without disrupting the printed shape and provide mechanical properties comparable with the high molecular weight latex polymer. As a result, this work introduces high molecular weight, high performance polymers to VP and reimagines latex applications beyond 2D coatings. Further investigations demonstrate the versatility of this approach beyond elastomers with successful implementations with glassy polymers and inorganic (silica) particles which yield nanocomposites.

Research interest in Additive Manufacturing (AM) as an enabling technology for customizable parts is rapidly expanding. While much AM research focus is on high performance feedstocks and process optimization to obtain parts with improved mechanical properties, interest in the environmental applications of AM has recently increased. The lower cost and greater accessibility AM is leading to novel environmental research solutions in wastewater treatment and toxicity reduction by capitalizing on the increased affordability and accessibility of 3D printing (3DP) technologies for customizable, high surface area structures. The novelty and focus of this dissertation is exploration of Material Extrusion (MatEx) based Fused Filament Fabrication (FFF) of filled polymer composites as a disruptive technology enabler for deployable and retrievable structures in environmental media for adsorption, destruction and toxicity reduction of harmful chemicals. This dissertation addresses research questions that generally answer, "why AM for environmental applications?". The inherent layer-by-layer design provides larger surface area structures for interaction with contaminated media. Polylactic acid (PLA) was selected due to its green sources and biocompatibility relative to synthetic polymers and its wide processing window allowing shear thinning and "printability" despite the elevated viscosity and modulus of highly filled composites. The filler selected for contaminant adsorption was microporous zeolite, which has affinity for ammonia, radionuclides and Per- and Polyfluorinated Substances (PFAS). The filler selected for contaminant destruction was photocatalytic TiO2 nanoparticles which can degrade organic chemicals, harmful algal bloom toxins and PFAS. A preliminary research hurdle was overcome by demonstrating that immobilization of zeolite and TiO2 in a PLA binder matrix did not prevent adsorption or free radical release, respectively. The first major research objective involved investigation of high surface area printed PLA-zeolite geometries with different zeolite loadings and found that while ammonia was reduced, there were diminishing returns with increased loading in terms of mass standardized adsorptive performance due to insufficiently exposed zeolite. The research solution leveraged AM print process parameters to increase the macroporosity of the printed composite structure to create voids and channels allowing water infiltration and chemical adsorption to zeolite. Faster printing of larger roadways generated macrostructural voids that were maintained by extrusion at lower temperature for rapid solidification. The second research objective involved compounding different loadings and dispersion states of TiO2 in PLA to demonstrate immobilization of TiO2 closer to UV-light penetration water improves photocatalysis. Higher 32% w/w TiO2 loadings were heavily agglomerated and more difficult to print process due to high viscosity, rapid liquid-solid transition (G'>G") and particle network recovery during printer retractions, leading to nozzle clogging. Lower 20% w/w loading was more conducive to larger production printing due to lower viscosity, longer viscosity recovery times for retractions and thus generally a wider processing window. While altering twin screw processing parameters reduced TiO2 agglomerates in filaments, leading to increases in crystallinity (due to seeding effects and chain scission) and lower viscosity recovery, photocatalytic performance was not significantly improved. Evidence presented showed that larger particle agglomerates were more toward the inside of printed surfaces and thus less available to UV-light irradiation. This location of larger particles is supported by previous theoretical and empirical investigations showing larger particles migrate at a faster velocity away from the outer walls of confined extrudates within non-Newtonian flow fields due to normal forces, leaving more smaller particles toward outer surfaces. This research provided novel contributions to the environmental and AM research communities and pioneered a convergence of these fields into an interdisciplinary community of practice focused on better characterization and processing in environmental applications to improve structure-environmental property relationships. Future research should build on these findings to enhance performance through multi-functional materials that adsorb and destroy contaminants. The reactive surface area should be further increased through by high surface area designs and print parameter optimized porous structures providing a continuum of meso- to microporosity as confirmed by chemical flux and mass transfer studies for additional AM technologies (e.g., Direct Ink Write). / Doctor of Philosophy / Engineers and hobbies alike have great interest in Additive Manufacturing (AM), or 3D Printing, to customize parts and new designs. More recently, environmental scientists and engineers have turned to 3D printing to solve environmental problems due to the lower cost and user-friendliness of desktop machines. This research dissertation focuses on how 3D printing can allow for iterative improvements in customizable, high surface area structures to reduce chemical concentrations in water by either adsorbing or destroying the chemicals. Water is clearly a critical resource for ecosystems, recreation and drinking supplies as national security, human and ecosystem health are tied to clean water. This research addresses why 3D printing is interesting and effective for environmental solutions. Briefly the layer-by-layer design provides larger surface area structures for interaction with contaminated media. The common 3D printer feedstock Polylactic Acid (PLA) was selected since it is non-toxic and can be relatively easy to print even if modified by adding rigid filler particles for research. Micron-scale (zeolite) and nano-scale (Titanium Dioxide) particles were mixed with the polymer to make printable filaments to adsorb and destroy contaminants, respectively. This research demonstrated the proof-of-concept by removing ammonia, methylene blue dye and a harmful algal toxin from water. The materials produced are also applicable to both conventional organic pollutants and emerging contaminants of concern in the popular news such as Per- and Polyfluorinated Substances (PFAS), which were used as flame retardants and non-stick surfaces. This research ties the material properties of the experimental micro- and nano-composite filaments to how the materials extrude and solidify during 3D printing and how well the resulting printed structures work for reducing contaminant levels in water. Altering the parameters and conditions at which these materials are processed and 3D printed can significantly change their structure, density, porosity and distribution of particles and in turn increase effectiveness. The results provide new contributions to both the environmental and AM research communities and pioneers interdisciplinary collaborative ideas for these different subject matter experts to work together to better understand how handling and processing of these materials can improve their performance in environmental applications. New work should leverage the ideas and principles presented here to further improve performance, ease of production and scale-up of multifunctional material structures for multiple classes of chemicals that are of concern in surface and drinking water.