Sandwich panels serve many purposes in engineering applications. Additive manufacturing opened the door for easy fabrication of the sandwich panels with different core structures. In this study, additive manufacturing technique, experiments, and numerical analysis are combined to evaluate the mechanical properties of sandwich panels with different cellular core structures. The sandwich panels having honeycomb, re-entrant honeycomb, diamond, square core topologies are printed with the vat photopolymerization technique. Uniaxial compression testing is performed to determine the compressive modulus, strength, and specific strength of these lightweight panels. Elasto-plastic finite element analysis having good similarities with the experimental results provided a preview of the stress distribution of the sandwich panels under applied loading. The imaging of the tested samples showed the fractured regions of the cellular cores. Dynamic mechanical analysis of the panels provided scope to compare the performance of panels and solid materials with the variation of temperature. Sandwich panels with the diamond structure exhibit better compressive properties and specific strength while the re-entrant structure offers high energy absorption capacity. The sandwich structures provided better thermo-mechanical properties than the solid material. The findings of this study offer insights into the mechanical properties of sandwich panels printed with vat photopolymerization technique which can benefit a wide range of engineering applications.

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.

Vat photopolymerization's (VP) use in large-scale industrial manufacturing is limited due to poor scalability, and limited catalogue of engineering polymers. The challenges in scalability stem from an inherent process paradox: the feature resolution, part size, and manufacturing throughput cannot be maximized simultaneously in standard VP platforms. In addition, VP's inability to process viscous and high-molecular weight engineering polymers limits the VP materials catalogue. To address these limitations, the research presented in this work was conducted in two stages: (1) Development and modeling of new VP platforms to address the scalability and viscosity challenges, and (2) Investigating the influence of using the new processes on the cured polymer network structure and mechanical properties. First, a scanning mask projection vat photopolymerization (S-MPVP) system was developed to address the scalability limitations in VP systems. The process paradox was resolved by scanning the mask projection device across the resin surface while simultaneously projecting the layer as a movie. Using actual projected pixel irradiance distribution, a process model was developed to capture the interaction between projected pixels and the resin, and predict the resulting cure profile with an error of 2.9%. The S-MPVP model was then extended for processing heterogeneous UV scattering resins (i.e. UV curable polymer colloids). Using computer vision, the scattering of incident UV radiation on the resin surface was successfully captured and used to predict scattering-compensated printing parameters (bitmap pattern, exposure time , scanning speed). The developed reverse-curing model was used to successfully fabricate complex features using photocurable SBR latex with XY errors < 1.3%. To address the low manufacturing throughput of VP systems, a recoat-less, volumetric curing VP system that fabricates parts by continuously irradiating the resin surface with a movie composed of different gray-scaled bitmap images ( Free-surface movie mask projection (FreeMMaP)) was developed. The effect of cumulative exposure on the cure profile (X,Y,Z dimensions) was investigated and used to develop an iterative gray-scaling algorithm that generated a combination of gray-scaled bitmap images and exposure times that result in accurate volumetric curing (errors in XY plane and Z axis < 5% and 3% respectively). Results of this work demonstrate that the elimination of the recoating process increased manufacturing speed by 8.05 times and enabled high-resolution fabrication with highly viscous resins or soft gels. Then, highly viscous resins were made processible in VP systems by using elevated processing temperatures to lower resin viscosity. New characterization techniques were developed to determine the threshold printing temperature and time that prevented the onset of thermally-induced polymerization. The effect of printing temperature on curing, cured polymer structure, cured polymer mechanical properties, and printable aspect ratio was also investigated using diacrylate and dimethacrylate resins. Results of this investigation revealed increasing printing temperature resulted in improvements in crosslink density, tensile strength, and printability. However, presence of hydroxl groups on the resin backbone caused deterioration of crosslink density, mechanical properties, and curing properties at elevated printing temperatures. Finally, the lack of a systematic, constraint based approach to resin design was bridged by using the results of earlier process-structure-property explorations to create an intuitive framework for resin screening and design. Key screening parameters (such as UV absorptivity, plateau storage modulus) and design parameters (such as photoinitiator concentration, polymer concentration, UV blocker concentration) were identified and the methods to optimize them to meet the desired printability metrics were demonstrated using case studies. Most work in vat photopolymerization either deal with materials development or process development and modeling. This dissertation is placed at the intersection of process development and materials development, thus giving it an unique perspective for exploring the inter-dependency of machine and material. The process models, machines and techniques used in this work to make a material printable will serve as a guide for chemists and engineers working on the next generation of vat photopolymerization machines and materials. / Doctor of Philosophy / Vat Photopolymerization (VP) is a polymer-based additive manufacturing platform that uses UV light to cure a photo-sensitive polymer into the desired shape. While parts fabricated via VP exhibit excellent surface finish and high-feature resolution, their use for commercial manufacturing is limited because of its poor scalability for large-scale manufacturing and limited selection of engineering materials. This work focuses on the development of new VP platforms, process models and the investigation of the process-structure-property relationships to mitigate these limitations and enable fabrication of performance polymers. The first section of the dissertation presents the development of two new VP platforms to address the limitations in scalability. The Scanning Mask Projection Vat Photopolymerization (S-MPVP)) was developed to fabricate large area parts with high-resolution features and the Free-surface movie mask projection (FreeMMaP) VP platform was developed to enable high-speed, recoat-less, volumetric fabrication of 3D objects. Computer-vision based models were developed to investigate the influence of these new processes on the resultant cure shape and dimensional accuracy. Process models that can: (1) predict the cure profile for given input printing parameters (error < 3%), (2) predict the printing parameters (exposure time, bitmap gray-scaling) required for accurate part fabrication in homogeneous and UV scattering resins, and (3) generate gray-scaled bitmap images that can induce volumetric curing inside the resin (dimensional accuracy of 97% Z axis, 95% XY axis), were designed and demonstrated successfully. In the second portion of this work, the use of high-temperature VP to enable processing of high-viscosity resins and expansion of materials catalogue is presented. New methods to characterize the resin's thermal stability are developed. Techniques to determine the printing temperature and time that will prevent the occurrence of thermally-induced polymerization are demonstrated. Parts were fabricated at different printing temperatures and the influence of printing temperature on the resultant mechanical properties and polymer network structure was studied. Results of this work indicate that elevated printing temperature can be used to alter the final mechanical properties of the printed part and improve the printability of the high-resolution, slender features. Finally, the results of the process-structure-property investigations conducted in this work were used to guide the development of a resin design framework that highlights the parameters, metrics, and methods required to (1) identify printable resin formulations, and (2) tune printable formulations for optimal photocuring. Elements of this framework were then combined into an intuitive flowchart to serve as a design tool for chemists and engineers.

<p dir="ltr">Though vat photopolymerization-based Additive manufacturing (AM) technology shows potential in fabricating complex optical components rapidly, its poor surface quality and dimensional accuracy render it unqualified for industrial optics applications. The layer steps in the building direction and the pixelated steps on each layer’s contour result in inevitable microscale defects on the 3D-printed surface, far away from the nanoscale roughness required for optics.</p><p dir="ltr">To tackle the lateral stair-stepping issue caused by the pixelated projection pattern, we propose to defocus the curing image pattern by increasing the gap between the light source and the resin vat. This gap intentionally blurs the disconnected pixels to create a continuous and smooth projection pattern. Experiments verified that the smoothened image pattern led to an average 81.2% reduction in surface roughness, which was much more effective than grayscale pixels. The gap between the light source screen and the resin vat also enabled blowing air to dissipate the heat from the resin polymerization, reducing the part distortion and printing failure due to the thermal stress.</p><p dir="ltr">The precision spin coating process is reported to solve vertical stair-stepping defects. We establish a mathematical model to predict and control the spin coating process on 3D-printed surfaces precisely. In this work, a precision aspherical lens is demonstrated with less than 1 nm surface roughness and 1 µm profile accuracy. The 3D-printed convex lens achieves a maximum MTF resolution of 347.7 lp/mm.</p><p dir="ltr">Leveraging this low-cost yet highly robust and repeatable 3D printing process, we showcase the precision fabrication of multi-scale spherical, aspherical, and axicon lenses with sizes ranging from 3 mm to 70 mm using high clear photocuring resins. Additionally, molds were also printed to form multi-scale PDMS-based lenses. Following precision polishing, precision machining, and precision molding, we anticipate that precision spin coating will empower 3D printing as the fourth generation of lens making and unleash the power of 3D-printed lenses in rapid and massive customization of high-quality optical components and systems.</p>

Polymer synthesis and functionalization enabled the tailoring of polymer functionality for additive manufacturing (AM), elastomer, and biological applications. Inspiration from academic and patent literature prompted an emphasis on polymer functionality and its implications on diverse applications. Critical analysis of existing elastomers for AM aided the synthesis and characterization of novel photopolymer systems for lithography-based 3D printing. Emphasis on structure-processing-property relationships facilitated the attainment of success in proposed applications and prompted further fundamental understanding for systems that leveraged poly(dimethyl siloxane)s (PDMS), aliphatic polyesters, polyamides, and polyethers for emerging applications. The thiol-ene reaction possesses many desirable traits for vat photopolymerization (VP) AM, namely that it proceeds rapidly to high yield, does not undergo significant side reactions, remains tolerant of the presence of water or oxygen, and remains regiospecific. Leveraging these traits, a novel PDMS-based photopolymer system was synthesized and designed that underwent simultaneous chain extension and crosslinking, affording relatively low viscosity prior to photocuring but the modulus and tensile strain at break properties of higher molecular weight precursors upon photocuring. A monomeric competition study confirmed chemical preference for the chain-extension reaction in the absence of diffusion. Photocalorimetry, photorheology, and soxhlet extraction measured photocuring kinetics and demonstrated high gel fractions upon photocuring. A further improvement on the low-temperature elastomeric behavior occurred via introduction of a small amount of diphenylsiloxane or diethylsiloxane repeating units, which successfully suppressed crystallization and extended the rubbery plateau close to the glass transition temperature (Tg) for these elastomers. Finally, a melt polymerization of PDMS diamines in the presence of a disiloxane diamine chain extender and urea afforded isocyanate-free polyureas in the absence of solvent and catalyst. Dynamic mechanical analysis (DMA) measured multiple, distinct α-relaxations that suggested microphase separation. This work leverages the unique properties of PDMS and provides multiple chemistries that achieve elastomeric properties for a variety of applications. Similar work of new polymers for VP AM was performed that leveraged the low Tg poly(propylene glycol) (PPG) and poly(tri(ethylene glycol) adipate) (PTEGA) for use in tissue scaffolding, footwear, and improved glove grip performance applications. The double endcapping of a PPG diamine with a diisocyanate and then hydroxyethyl acrylate provided a urethane/urea-containing, photocurable oligomer. Supercritical fluid chromatography with evaporative light scattering detection elucidated oligomer molecular weight distributions with repeat unit resolution, while the combination of these PPG-containing oligomers with various reactive diluents prior to photocuring yielded highly tunable and efficiently crosslinked networks with wide-ranging thermomechanical properties. Functionalization of the PTEGA diol with isocyanatoethyl methacrylate yielded a photocurable polyester for tissue scaffolding applications without the production of acidic byproducts that might induce polymer backbone scission. Initial VP AM, cell viability experiments, and modulus measurements indicate promise for use of these PTEGA oligomers for the 3D production of vascularized tissue scaffolds. Similar review of powder bed fusion (PBF) patent literature revealed a polyamide 12 (PA12) composition that remained melt stable during PBF processing, unlike alternative commercial products. Further investigation revealed a fundamental difference in polymer backbone and endgroup chemical structure between these products, yielding profound differences for powder recyclability after printing. An anionic dispersion polymerization of laurolactam in the presence of a steric stabilizer and initiator yielded PA12 microparticles with high sphericity directly from the polymerization without significant post-processing requirements. Steric stabilizer concentration and stirring rate remained the most important variables for the control of PA12 powder particle size and melt viscosity. Finally, preliminary fusion of single-layered PA12 structures demonstrated promise and provided insight into powder particle size and melt viscosity requirements. / PHD / Additive manufacturing (AM) enables the creation of unique geometries not accessible with alternative manufacturing techniques such as injection molding, while also reducing the waste associated with subtractive manufacturing (e.g. machining). However, AM currently suffers from a lack of commercially-available polymers that provide elastomeric properties after processing. Poly(dimethyl siloxane)s (PDMS) possess distinctive properties due to their organosilicon polymer backbone that include chemical inertness, non-flammability, high gas permeability, and low surface energy. For these reasons, siloxanes enjoy wide-ranging applications from personal care products, contact lenses, elastomeric sealants, and medical devices. This dissertation focuses on the synthesis and functionalization of novel PDMS-, polyether-, polyester-, and polyamide-containing photopolymers or powders for improved performance in diverse applications that employ processing via vat photopolymerization (VP) or powder bed fusion (PBF) AM. Examples from this work include a novel photopolymer composition that undergoes simultaneous chain extension and crosslinking, affording low molecular weight and low viscosity precursors prior to VP-AM but the properties of higher molecular weight precursors, once photocured. Related work involved the characterization and VP-AM of siloxane terpolymers that suppress crystallization normally observed in PDMS, resulting in 3D printed objects that retain their elastomeric properties close to the glass transition temperature (Tg). Separate work leveraged the unique PDMS backbone for the melt polymerization of PDMS diamines in the presence of a chain extender and urea, yielding isocyanate-free PDMS polyureas in the absence of solvent or catalyst. This reaction creates ammonia as the only by-product and avoids the use of isocyanates, as well as their highly toxic precursors, phosgene. Finally, another research direction facilitates the understanding of observed differences in melt stability between commercially-available grades of polyamide 12 (PA12) powders for powder bed fusion. An anionic dispersion polymerization based in the patent literature facilitated further understanding of the polymerization process and produced melt-stable PA12 microparticles directly from the polymerization process, without requiring additional post-processing grinding or precipitation steps for powder production.

The reliance on low-viscosity and photoactive resins limits the accessible properties for vat photopolymerization (VP) materials required for engineering applications. This has limited the adoption of VP for producing end-use parts, which typically require high MW polymers and/or more stable chemical functionality. Decoupling the viscosity and molecular weight relationship for VP resins has been completed recently for polyimides and highperformance elastomers by photocuring a scaffold around polymer precursors or polymer nanoparticles, respectively. Both of these materials are first shaped by printing a green part followed by thermal post-processing to achieve the final part properties. This dissertation focuses on improving the processability of these material systems by (i) investigating the impact of scaffold architecture and polysalt monomer composition on photocuring, thermal post-processing, and resulting thermomechanical properties and (ii) developing a Monte Carlo ray-tracing (MCRT) simulation to predict light scattering and photocuring behavior in particle-filled resins, specifically zinc oxide nanoparticles in a rigid polyester resin and styrene butadiene rubber latex resin. The first portion of the dissertation introduces VP of a tetra-acid and half-ester-based polysalt resin derived from 4,4'-oxydiphthalic anhydride and 4,4-oxydianiline (ODPA-ODA), a fully aromatic polyimide with high glass transition temperature and thermal stability. This polyimide, and polyimides like this, find use in demanding industries such as aerospace, automotive and electronic applications. The author evaluated the hypothesis that a non-bound triethylene glycol dimethacrylate (TEGDMA) scaffold would facilitate more efficient scaffold burnout and thus achieve parts with reduced off-gassing potential at elevated temperatures. Both resins demonstrated photocuring and were able to print solid and complex latticed parts. When thermally processed to 400 oC, only 3% of the TEGDMA scaffold remained within the final parts. The half-ester resin exhibits higher char yield, resulting from partial degradation of the polyimide backbone, potentially caused by lack of solvent retention limiting the imidization conversion. The tetra-acid exhibits a Tg of 260oC, while the half-ester displays a higher Tg of 380 oC caused by the degradation of the polymer backbone, forming residual char, restricting chain mobility. Solid parts displayed a phase-separated morphology while the half-ester latticed parts appear solid, indicating solvent removal occurs faster in the half-ester composition, presumably due to reduced polar acid functionality. This platform and scaffold architecture enables a modular approach to produce novel and easily customizable UV-curable polyimides to easily increase the variety of polyimides and the accessible properties of printed polyimides through VP. The second section of this dissertation describes the creation and validation of a MCRT simulation to predict light scattering and the resulting photocured shape of a ZnO-filled resin nanocomposite. Relative to prior MCRT simulations in the literature, this approach requires only simple, easily acquired inputs gathered from dynamic light scattering, refractometry, UV-vis spectroscopy, beam profilometry, and VP working curves to produce 2D exposure distributions. The concentration of 20 nm ZnO varied from 1 to 5 vol% and was exposed to a 7X7 pixel square ( 250 µm) from 5 to 11 s. Compared to experimentally produced cure profiles, the MCRT simulation is shown to predict cure depth within 10% (15 µm) and cure widths within 30% (20 µm), below the controllable resolution of the printer. Despite this success, this study was limited to small particles and low loadings to avoid polycrystalline particles and maintain dispersion stability for the duration of the experiments. Expanding the MCRT simulation to latex-based resins which are comprised of polymer nanoparticles that are amorphous, homogeneous, and colloidally stable. This allows for validating the MCRT with larger particles (100 nm) at higher loadings. Simulated cure profiles of styrene-butadiene rubber (SBR) loadings from 5 vol% to 25 vol% predicted cure depths within 20% ( µm) and cure widths within 50% ( µm) of experimental values. The error observed within the latex-based resin is significantly higher than in the ZnO resin and potentially caused by the green part shrinking due to evaporation of the resin's water, which leads to errors when trying to experimentally measure the cure profiles. This dissertation demonstrates the development of novel and functional materials and creation process-related improvements. Specifically, this dissertation presents a materials platform for the future development of unique photocurable engineering polymers and a corresponding physics-based model to aid in processing. / Doctor of Philosophy / Vat Photopolymerization (VP) is a 3D printing process that uses ultraviolet (UV) light to selectively cure liquid photosensitive resin into a solid part in a layer-by-layer fashion. Parts produced with VP exhibit a smooth surface finish and fine features of less than 100 µm (i.e., width of human hair). Recoating the liquid resin for each layer limits VP to low-viscosity resins, thus limiting the molecular weight (and thus performance) of the printed polymers accessible. Materials that are low molecular weight are limited in achieving desirable properties, such as elongation, strength, and heat resistance. Solvent-based resins, such as polysalt and latex resins have demonstrated the ability to decouple the viscosity and molecular weight relationship by eliminating polymer entanglements using low-molecular-weight precursors or isolating high-molecular-weight polymers into particles. This dissertation focuses on expanding and improving the printability of these methods. The second chapter of the dissertation investigates the impact of scaffold architecture in printing polyimide polysalts to improve scaffold burnout. Polysalts are polymers that exist as dissolved salts in solution, with each monomer holding two electronic charges. When heated, the solvent evaporates and the monomers react to form a high molecular-weight polymer. While previous work featured a polysalt that was covalently bonded to the monomers, the polysalt in this work is made printable by co-dissolving a scaffold. The polysalt resins are photocured and thermally processed to polymerize and imidize into a high-molecular-weight polymer, while simultaneously pyrolyzing the scaffold. Using a co-dissolved scaffold allows the investigation of two different monomers of tetra-acid and half-ester functionality. The half-ester composition underwent degradation during heating, increasing the printed parts' glass transition or softening point. The scaffold had little impact on the polysalt polymerization or final part properties and was efficiently removed, with only 3% remaining in final parts. The composition and properties of the monomers selected played a bigger role due to partial degradation altering the properties of the final parts. Overall, this platform and scaffold architecture allows for a larger number of polyimides to be accessible and easily customizable for future VP demands. The third chapter describes the challenges of processing photocurable resins that contain particles due to the UV light scattering in the resin vat during printing. When the light from the printer hits a particle, it is scattered in all directions causing the layer shape to be distorted from the designed shape. To overcome this, a Monte Carlo ray-tracing (MCRT) simulation was developed to mimic light rays scattering within the resin vat. The simulation was validated by comparing simulation results against experiment trials of photocuring resins containing 20nm zinc oxide (ZnO) nanoparticles. The MCRT simulation predicted all the experimental cure depths within 10% (20 µm) and cured widths within 30% (15 µm) error. Despite the high accuracy, this study was limited to small particles and low concentrations. Simulating larger particles is difficult as the simulation assumes each particle to be uniform throughout its volume, which is atypical of large ceramic particles. The fourth chapter enables high particle volume loading by using a highly stretchable styrene-butadiene rubber (SBR) latex-based resin. Latex-based resins maintain low viscosity by separating large polymer chains into nano-particles that are noncrystalline and uniform. When the chains are separated, they cannot interact or entangle, keeping the viscosity low even at high concentrations (>30 vol%). Like the ZnO-filled resin, the latex resin is experimentally cured and the MCRT simulation predicts the resulting cure shape. The MCRT simulation predicted cure depths within 20% (100 µm) and over-cure widths within 50% (100 µm) of experimental values. This error is substantially higher than the ZnO work and is believed to be caused by the water evaporating from the cured resin resulting in inconsistent measurements of the cured dimensions.

Additive manufacturing (AM) creates 3D objects out of polymers, ceramics, and metals to enable cost-efficient and rapid production of products from aerospace to biomedical applications. Personalized products manufactured using AM, such as personalized dosage pharmaceuticals, tissue scaffolds, and medical devices, require specific material properties such as biocompatibility and biodegradability, etc. Polymers possess many of these qualities and tuning molecular structure enables a functional material to successfully deliver the intended application. For example, water-soluble polymers such as poly(vinyl pyrrolidone) and poly(ethylene glycol) both function as drug delivery materials because of their inherit water-solubility and biocompatibility. Other polymers such as polylactide and polyglycolide possess hydrolytically cleavable functionalities, which enables degradation in the body. Non-covalent bonds, such as hydrogen bonding and electrostatic interactions, enable strong connections capable of holding materials together, but disconnect with heat or solvation. Taking into consideration some of these polymer functionalities, this dissertation investigates how to utilize them to create functional biomedical products using AM. The investigation of structure-property-processing relationships of polymer molecular structures, physical properties, and processing behaviors is transforming the field of new materials for AM. Even though novel, functional materials for AM continue to be developed, requirements that render a polymeric material printable remain unknown or vague for most AM processes. Materials and printers are usually developed separately, which creates a disconnect between the material printing requirements and fundamental physical properties that enable successful printing. Through the interface of chemistry, biology, chemical engineering, and mechanical engineering, this dissertation aims to relate printability of polymeric materials with three types of AM processes, namely vat photopolymerization, binder jetting, and powder bed fusion. Binder jetting, vat photopolymerization, and powder bed fusion require different viscosity and powder requirements depending on the printer capabilities, and if the material is neat or in solution. Developing scaling relationships between solution viscosity and concentration determined critical overlap (C*) and entanglement (Ce) concentrations, which are related to the printability of the materials. For example, this dissertation discusses and investigates the maximum printable concentration in binder jetting of multiple polymer architectures in solution as a function of C* values of the polymer. For thermal-type printheads, C* appeared to be the highest jettable concentration, which asserted an additional method of material screening for binder jetting. Another investigation of the photokinetics as a function of concentration of photo-active polymers in solution revealed increased viscosity leads to decreased acrylate/acrylamide conversion. Lastly, investigating particle size and shape of poly(stearyl acrylate) particles synthesized through suspension polymerization revealed a combination of crosslinked and linear polymers produced high resolution parts for phase change materials. These analytical screening methods will help the progression of AM and provide future scientists and engineers a better guideline for material screenings. / Doctor of Philosophy / Additive manufacturing (AM), also known as 3D printing, enables the creation of 3D objects in a rapid and cost-efficient manner for applications from aerospace to biomedical sectors. AM particularly benefits the field of personalized biomedical products, such as personalized dosage pharmaceuticals, hearing aids, and prosthetic limbs. In the future, advanced detection and prevention medical screenings will provide doctors, pharmacists, and engineers very precise data to enable personalized healthcare. For example, a patient can take three different medications in one pill with the exact dosage to prevent side-effects and drug-drug interactions. AM enables the delivery and manufacturing of these personalized systems and will improve healthcare in every sector. Investigations of the most effective materials is needed for personalized medicine to become a reality. Polymers, or macromolecules, provide a highly tunable material to become printable with slight chemical modifications. Investigation of how chemical structure affects properties, such as strength, stretchability, or viscosity, will dictate how they perform in a manufacturing setting. This process of investigation is called "structure-property-processing" relationships, which connects scientists and engineers through all disciplines. This method is used to discover which polymers will not only 3D print, but also carry medication to a patient or deliver therapeutics within the body.

No description available.

Ultrasound directed self-assembly (DSA) utilizes the acoustic radiation force associated with a standing ultrasound wave field to organize particles dispersed in a fluid medium into specific patterns. The ability to tailor the organization and packing density of spherical particles using ultrasound DSA in a viscous fluid medium is crucial in the context of (additive) manufacturing of engineered materials with tailored properties. However, the fundamental physics of the ultrasound DSA process in a viscous fluid medium, and the relationship between the ultrasound DSA process parameters and the specific patterns of particles that result from it, are not well-understood. Researchers have theoretically described the acoustic radiation force and the acoustic interaction force that act on spherical particles in a standing ultrasound wave field in both inviscid and viscous media. In addition, they have solved the forward and inverse ultrasound DSA problem in an inviscid medium, in which they relate the patterns of particles and the ultrasound DSA operating parameters. However, no theoretical model exists that allows simulating the steady-state and transient local particle packing density in a viscous medium during ultrasound DSA. Thus, in this dissertation, we (i) theoretically derive and experimentally validate a model to determine the steady-state locations where spherical particles assemble during ultrasound DSA as a function of medium viscosity and particle volume fraction. (ii) We also theoretically derive and experimentally validate a model to quantify the steady-state and transient local packing density of spherical particles within the pattern features that result from ultrasound DSA. Using these models, we quantify and predict the locations where spherical particles assemble during ultrasound DSA in a viscous medium, considering the effects of medium viscosity and particle volume fraction. We demonstrate that the deviation between locations where particles assemble in viscous and inviscid media first increases and then decreases with increasing particle volume fraction and medium viscosity, which we explain by means of the sound propagation velocity of the mixture. In addition, we quantify and predict the steady-state and transient local packing density of spherical particles within the pattern features, using ultrasound DSA in combination with vat photopolymerization (VP). We show that the steady-state local particle packing density increases with increasing particle volume fraction and increases with decreasing particle size. We also show that the transient local particle packing density increases with increasing particle volume fraction, decreasing particle size, and decreasing fluid medium viscosity. Increasing particle size and decreasing fluid medium viscosity decreases the time to reach steady-state. Finally, we implement single and multiple scattering in the calculation of the acoustic radiation force for spherical particles in a viscous medium and quantify their relative contributions to the calculation of the acoustic radiation force as a function of ultrasound DSA operating parameters and material properties. We demonstrate that the deviation between considering single and multiple scattering may reach up to 100%, depending on the ultrasound DSA process parameters and material properties. Also, increasing the particle volume fraction increases the need to account for multiple scattering. Quantifying and predicting the local packing density of spherical particles during ultrasound DSA in a viscous medium, as a function of ultrasound DSA process parameters is crucial towards using ultrasound DSA in engineering applications, in particular (additive) manufacturing of engineered polymer matrix composite materials with tailored properties whose properties depend on the spatial organization and packing density of particles in the matrix material. / Doctor of Philosophy / Ultrasound directed self-assembly (DSA) is a technique that uses ultrasound waves to arrange small particles submerged in a fluid into specific patterns. When combined with other manufacturing techniques, ultrasound DSA can be used to fabricate composite materials that derive their properties from the spatial organization of particles in a matrix material. However, ultrasound DSA in viscous fluids is not well-understood. Researchers have studied the forces associated with ultrasound waves that move small spherical particles in an inviscid fluid medium (fluids that experience little to no internal resistance to flow), and they have demonstrated intricate control of the patterns of particles that form using ultrasound DSA. However, that knowledge is not currently available for ultrasound DSA in viscous media. In this dissertation, we develop and evaluate theoretical models to understand ultrasound DSA of small spherical particles in a viscous fluid medium. We simulate where particles organize and how densely they pack together. We also determine the difference of the time-dependent motion of particles in a viscous fluid compared to that in an inviscid fluid medium and relate the difference to the number of particles submerged in the fluid and the viscosity of the fluid. Additionally, we examine the effect of particle size and fluid viscosity on the speed by which the particles reach their final location. We also study how ultrasound waves interact with multiple small particles in a viscous fluid, focusing on the forces that move these particles. We explore two models that account for single and multiple ultrasound wave scattering. Scattering is the process by which ultrasound waves deflect in different directions when they encounter a particle. The results show that the difference between single and multiple scattering models can be significant, depending on the ultrasound DSA process parameters and the properties of the fluid and particles. In general, the importance of accounting for multiple scattering increases with the number of particles submerged in the fluid. Understanding particle packing density when using ultrasound DSA in a viscous fluid is essential in many engineering applications, in particular manufacturing of composite materials that derive their properties from the spatial arrangement of particles in a matrix material.

Multiphase systems provide an opportunity to develop both novel processing methods and create advanced materials through combining the properties of dissimilar phases in a synergistic manner. In this work, we detail the halogenation of poly(ether ether ketone) (PEEK) through both solution-state and gel-state functionalization methods. The multiphase gel-state chemistry restricts functionalization to the amorphous regions of the semi-crystalline parent homopolymer and generates a copolymer with a blocky microstructure. Solution-state functionalization yields random copolymers which provide matched sets to the blocky analogs for fundamental investigations into the effects of polymer microstructure on material properties. Halogenating PEEK using N-halosuccinimides allows for direct installation of pendant halogens along the polymer backbone with facile control of halogen identity. For both bromination and iodination, blocky halogenation of PEEK provides faster crystallization kinetics, higher glass transition (Tg) and melting temperatures as well as superior crystallizability than random halogenation. When comparing halogen identity, increasing halogen size results in increased Tgs, decreased backbone planarity, and for copolymers with blocky microstructures, an earlier onset of phase separation. Increasing halogen size also results in decreased crystallizability and crystallization kinetics, however, these deleterious effects are mitigated in blocky microstructures due to colocalization of the pristine repeat units. Iodination also results in greater flame resistance than bromination for PEEK-based copolymers, and preserved crystallizability allows for the generation of flame retardant aerogels. Direct halogenation of PEEK in the gel-state also provided a reactive microstructural template for subsequent functionalization. Through the use of copper mediated cross-coupling chemistries, the aryl halide functionalities were leveraged to decorate the polymer backbone with pendant perfluoroalkyl chains. The blocky perfluoro alkyl PEEK demonstrated preserved crystallizability and serves as a candidate for compatibilization of poly(tetrafluoroethylene)-PEEK polymer blends. Superacid-modified PEEK was synthesized through a similar methodology and demonstrated over 50,000% increased hygroscopicity relative to the parent homopolymer, and exhibited preserved crystallizability. Multiphase systems were also designed to additively manufacture reinforced elastomers through vat photopolymerization using a degradable scaffold approach that challenged the current paradigm that the scaffold only serves as a geometrical template in vat photopolymerization. The scaffold crosslinks were cleaved through a reactive extraction process that liberated the glassy photopolymer backbone and resulted in over 200% increased ultimate strain and 50% increased ultimate stress relative to a control that was subjected to a neutral extraction. Lastly, thermoresponsive micellar ligands were synthesized as a multiphase approach to environmental remediation of metal-contaminated aqueous systems. / Doctor of Philosophy / Multiphase systems, such as a mixture of oil and water, are of great interest due to their ability to exhibit a multitude of properties from one material. Minimizing the size of the phases, through a technique called compatibilization, often improves the properties of the material. A common example is salad dressing, where the oil phase is compartmentalized into microscopic particles using surface-active molecules known as surfactants. Surfactants, also known as amphiphiles, partition to the interface between different phases due to the surfactants being comprised of dissimilar molecular constituents. One way to generate polymeric amphiphiles, where a polymer is a large molecule comprised of a molecular chain of repeating units, is through synthesizing block copolymers. Block copolymers have blocks of different constituents that are colocalized through covalent bonds in the polymer backbone and often exhibit phase separated structures, allowing for enhanced transport properties such as is seen in membranes. Using semi-crystalline polymers in membranes allows for enhanced mechanical integrity, as the crystallites act as physical crosslinks, or tie points, similar to the knots in a 3D rope ladder. These molecular knots limit the distance that the linear segments of the rope ladder can stretch, which in membranes leads to reduced swelling and increased mechanical performance. In this work we use semi-crystalline polymers to generate blocky copolymers through the use of halogenation. Halogenation installs halogen moieties as pendant groups on the polymer backbone, which can then by used as a chemical handle for subsequent reactions to further incorporate functionality into the copolymer and achieve desired properties such as proton (hydrogen nuclei) transport in fuel cell membranes. Halogenation also allows for the generation of blocky semi-crystalline copolymers for compatibilizing polymer blends of materials like poly(tetrafluoroethylene) and poly(ether ether ketone). Also in this work, we discuss the additive manufacturing of mechanically reinforced elastomers. An elastomer is another type of crosslinked network, and a mechanically reinforced elastomer can be through of as a 3D rope ladder where some of the linear segments of rope are replaced with steel bars, thus increasing the amount of work required to deform the network. The last multiphase systems discussed are similar to salad dressing, where there is a continuous water phase and a microscopic particle phase. The microscopic particles in this work are amphiphilic block copolymers that change their solubility in water with temperature and also have functionalities that should allow for the binding of metals from water-based systems.