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High-speed operatorless photographic printers require high illumination levels at the negative print gate from lamps with stable color temperatures. The lamps using in these applications give off a large amount of heat radiation that is harmful to photographic emulsions as well as printer components and must be removed. This report describes how a typical photographic printer lamphouse separates the visible energy from the infrared, delivers the visible energy to the negative to be printed, and removes the infrared energy from the housing. This report also develops a set of empirically derived equations, which analytically describe the cooling mechanisms. These equations are intended to be useful design tools in future printer lamphouse development.

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.

Perovskite solar cells have attracted much attention both in research and industrial domains. An unprecedented progress in development of hybrid perovskite solar cells (HPSCs) has been seen in past few years. The power conversion efficiencies of HPSCs has been improved from 3.8% to 24.2% in less than a decade, rivaling that of silicon solar cells which currently dominate the solar cell market. Hybrid perovskite materials have exceptional opto-electrical properties and can be processed using cost-effective solution-based methods. In contrast, fabrication of silicon solar cells requires high-vacuum, high-temperature, and energy intensive processes. The combination of excellent opto-electrical properties and cost-effective manufacturing makes hybrid perovskite a winning candidate for solar cells. As power conversion efficiencies of HPSCs improves beyond that of the established solar cell technology and their long-term stability increases, one of the crucial hurdles in the path to commercialization remaining to be adequately addressed is the cost-effective scalable fabrication. Spin-coating is the prevailing method for fabrication of HPSCs in laboratories. However, this technique is limited to small areas and results in excessive material waste. Two types of scalable manufacturing methods have been successfully demonstrated to fabricate HPSCs: (i) meniscus-assisted coating such as doctor-blade coating and slot-die coating; and (ii) dispersed deposition based on the coalescence of individual droplets, such as inkjet printing and spray coating. Electrospray printing belongs to the second category with advantages of high material utilization rate and patterning capability along with the scalability and roll-to-roll compatibility. In Chapter 3 of this dissertation, electrospray printing process is described for manufacturing of HPSCs in ambient conditions below 150 C. All three functional layers were printed using electrospray printing including perovskite layer, electron transport layer, and hole transport layer. Strategies for successful electrospray printing of HPSCs include formulation of the precursor inks with solvents of low vapor pressures, judicial choice of droplet flight time, and tailoring the wetting property of the substrate to suppress coffee ring effects. Implementation of these strategies leads to pin-hole free, low surface roughness, and uniform perovskite layer, hole transport layer and electron transport layer. The power conversion efficiency of the all electrospray printed device reached up to 15.0%, which is among the highest to date for fully printed HPSCs. The most efficient HPSCs rely on gold and organic hole-transport materials (HTMs) for achieving high performance. Gold is also chosen for its high stability. Unfortunately, the high price of gold and high-vacuum along with high-temperature processing requirements for gold film is not suitable for the large-scale fabrication of HPSCs. Carbon is a cheap alternative electrode material which is inert to hybrid perovskite layer. Due to the ambipolar transport property of hybrid perovskite, perovskite itself can act as a hole conductor, and the extra hole transport layer can be left out. Carbon films prepared by doctor-blade coating method have been reported as the top electrode in HPSCs. The efficiencies of these devices suffer from the poor interface between the doctor-blade coated carbon and the underlying perovskite layer. In Chapter 4, electrospray printing was applied for the fabrication of carbon films and by optimizing the working distance during electrospray printing, the interface between carbon and the underlying perovskite layer was greatly improved compared to the doctor-blade coated carbon film. The resulting HPSCs based on the electrospray printed carbon electrode achieved higher efficiency than that based on doctor-blade method and remarkably, this performance is close to that of gold based devices. In Chapter 5, preliminary results are provided on the laser annealing of hybrid perovskite films to further advance their scalable manufacturing. All layers of HPSCs require thermal annealing at temperature over 150 C for about half an hour or longer. The time-consuming conventional thermal annealing complicates the fabrication process and is not suitable for continuous production. High temperature over150 C is also not compatible with flexible substrates such as PET. Laser annealing is a promising method for overcoming these issues. It has several other advantages including compatibility with continuous roll-to-roll printing, minimal influence on non-radiated surrounding area, and rapid processing. Laser annealing can be integrated with the electrospray process to realize the continuous fabrication of hybrid perovskite film. Rapid laser annealing process with optimized power density and scanning pattern is demonstrated here for annealing perovskite films. The resulting hybrid perovskite film is highly-crystalline and pin-hole free, similar to that obtained from conventional thermal annealing. / Doctor of Philosophy / Hybrid perovskite solar cell (HPSC) is a promising low-cost and high efficiency photovoltaic technology. One of the big challenges for it to be commercially competitive is scalable fabrication method. This dissertation focuses on developing electrospray printing technology for HPSCs. This is a scalable method with high material usage rate that naturally lead to large scale fabrication of HPSCs. Electrospray printing parameter space was systematically studied and optimized to synthesize high-quality perovskite films and other functional layers including hole transport layer and electron transport layer. All electrospray printed high-efficiency perovskite solar cell devices were successfully demonstrated under the ambient condition and low temperature. Another achievement of this thesis is the electrospray printing of carbon film to replace the costly gold electrode in perovskite solar cells. Laser annealing technique is demonstrated for HPSCs, which is compatible with continuous fabrication and integrates easily with electrospray printing.

Additive Manufacturing (AM) provides a unique opportunity for fabrication of personalized medicine, where each oral dosage could be tailored to satisfy specific needs of each individual patient. Binder jetting, an easily scalable AM technique that is capable of processing the powdered raw material used by tablet manufacturers, is an attractive means for producing individualized pharmaceutical tablets. However, due to the low density of the printed specimens and incompatible binder-powder combination, tablets fabricated by this AM technology suffer from poor strength. The research is introducing an additional composition in the binder jetting powder bed (e.g., powdered sugar) could significantly enhance the compressive strength of the as-fabricated tablets, as compared with those tablets fabricated without the additional powder binding agent. However, no previous research demonstrated comprehensive approaches to enhance the poor performance of the 3D printed tablets. Therefore, the goal of this work is to identify processing techniques for improving the strength of binder jetted tablets, including the use of (i) novel jettable polymeric binders (e.g., 4-arm star polyvinylpyrrolidone (PVP), DI water, and different i) weight percentage of sorbitol binder) and (ii) introducing an additional powder binding agent into the powder bed (e.g.., different wt% of powdered sugar). / M.S. / Three-dimensional printing is well-known as 3D printing. 3D printing pills are printed from the 3D printer. As of today, we now stand on the brink of a fourth industrial revolution. By the remarkable technological advancements of the twenty-first century, manufacturing is now becoming digitized. Instead of using a large batch process as traditional, customized printlets with a tailored dose, shape, size, and release characteristics could be produced on- demand. The goal of developing pharmaceutical printing is to reduce the cost of labor, shorten the time of manufacturing, and tailor the pills for patients. And have the potential to cause a paradigm shift in medicine design, manufacture, and use. This paper aims to discuss the current and future potential applications of 3D printing in healthcare and, ultimately, the power of 3D printing in pharmaceuticals.

Gelatin methacrylate (GelMA) is a ubiquitous biocompatible photopolymer used in tissue engineering and regenerative medicine due to its cost-effective synthesis, tunable mechanical properties, and cellular response. Biotechnology applications utilizing GelMA have ranged from developing cell-laden hydrogel networks to cell encapsulation and additive manufacturing (3D printing). However, extrusion based 3D printing is the most common technique used with GelMA. Mask projection microstereolithography (MPµSL or µSL) is an advanced 3D printing technique that can produce geometries with high resolution, high complexity, and feature sizes unlike extrusion based printing. There are few biomaterials available for µSL applications, so 3D printing GelMA using µSL would not only add to the repertoire materials, but also demonstrate the advantages of µSL over other 3D printing techniques. A novel GelMA resin was tested with µSL to create a porous scaffold with a height and print time that has not been displayed in the literature before for a scaffold of this size. The resin consists of GelMA, deionized water, lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP, photoinitiator), and 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid (sulisobenzone, UV blocker) and can be processed at room temperature. Four resins were tested (w/w %) and characterized for µSL printing: 20% GelMA 0.5% UV blocker, 20% GelMA 1.0% UV blocker, 30% GelMA 0.5% UV Blocker, and 30% GelMA 1.0% UV blocker. Swell testing, working curve, photo-rheology, photo-DSC (dynamic scanning calorimetry), 3D printing, and cell culture tests were performed and results showed that 30% GelMA 1.0% UV blocker had the best 3D print fidelity among resin compositions. / Master of Science / Three dimensional (3D) printing is a widely used technology to rapidly produce structures with varying degrees of complexity. 3D printing of biological components is of interest because as the world population increases, there is a lack of donors available to compensate for organ loss and tissue replacement. 3D printing offers a solution to great custom scaffolds and structures that mimic physiological geometry and properties. One printing technique is known as microstereolithography, or µSL, which uses a projector-like system to pattern ultraviolet (UV) light in specific arrangements to generate complex geometries and 3D parts. Gelatin is a material of interest for this technology because gelatin is derived from collagen, which is the most abundant protein found in the body. Gelatin can be modified so that it is reactive with UV light, and can be processed with µSL to generate 3D structures. In this work, gelatin was modified into the form of gelatin methacrylate (GelMA) in order to develop and test resin formulations for use with µSL. Four different resins were tested and characterized and the results indicated that one GelMA resin produced prints with greater fidelity and resolution than other formulations. This resin has been identified for potential applications in tissue engineering and 3D printed organ development.

Hybridizing additive manufacturing (AM) structures and direct write (DW) deposition of conductive traces enables the design and physical creation of integrated, complex, and conformal electronics such as embedded electronics and complex routing on a fully AM structure. Although this hybridization has a promising outlook, there are several key AM substrate-related limitations that limit the final performance of these hybridized AM-DW electronic parts. These limitations include low-temperature processability (leading to high trace resistivity) and poor surface finish (leading to electronic shorts and disconnections). Recently discovered ultraviolet-assisted direct ink write (UV-DIW) all-aromatic polyimide (PI) provides an opportunity to address these previous shortcomings previously due to its high-temperature stability (450C) and superior surface finish (relative to other AM processes). The primary goal of this thesis is to characterize the integration of this UV-DIW PI with DW-printed conductive inks as a means for obtaining high-performance hybrid AM-DW electronics. This goal has been achieved through an investigation into the increased temperature stability of AM PI on the conductivity and adhesion of DW extrusion and aerosol jet (AJ) silver inks, determining the dielectric constant and dissipation factor of processed UV-DIW PI, and determining the achievable microwave application performance of UV-DIW PI. These performance measurements are compared to commercially-available PI film and relative to existing AM substrates, such as ULTEM 1010. The temperature stability of UV-DIW PI enabled higher-temperature post-processing for the printed silver traces, which decreased DIW trace resistivity from 14.94±0.55 times the value of bulk silver at 160 °C to 2.16±0.028 times the resistivity of bulk silver at 375 °C, and AJ silver trace resistivity from 5.27±0.013 times the resistivity of bulk silver at 200 °C to 1.95±0.15 times the resistivity of bulk silver at 350 °C. The adhesion of these traces was not negatively affected by higher processing temperatures, and the traces performed similarly on UV-DIW PI and commercial PI. Furthermore, at similar thicknesses, UV-DIW PI was found to have a similar dielectric constant and dissipation factor to commercial Dupont Kapton PI film from 1 kHz to 1 MHz, indicating its ability to perform highly as a dielectric electronics substrate. Finally, the decrease in resistivity was able to decrease the gap in microwave stripline transmission line performance when compared with ULTEM 1010 processed at 200°C, with peak 10 GHz S21 loss differences decreasing from 2.46 dB to 1.32 dB after increasing the UV-DIW processing temperature from 200 °C to 400°C. / Master of Science / Due to the extensive potential benefits and applications, researchers are looking to hybridize additive manufacturing (AM) processes with direct write (DW) techniques to directly print a 3D part with integrated electronics. Unfortunately, there are several key substrate-related limitations that hinder the overall performance of a part fabricated by hybrid AM-DW processes. Specifically, typical AM materials are not capable of providing an electronics substrate with combined sufficient surface resolution, surface finish, and high-temperature processing stability. However, the recent discovery of a novel AM-processable all-aromatic polyimide (PI) presents an opportunity for addressing these limitations as its printed form offers a high surface resolution, superior surface finish, and mechanical stability up to 400 °C. The primary goal of this thesis is to evaluate the benefits and drawbacks of this PI, processed via ultraviolet-assisted direct ink write (UV-DIW) AM, as an AM-DW electronics substrate. Specifically, the author characterized the effect of the increased temperature stability of the printed PI on the resultant conductivity and adhesion of silver inks printed via direct ink write (DIW) and aerosol jetting (AJ) DW processes. These results were also compared to the performance of the inks on commercial PI. Furthermore, the dielectric performance of printed PI was evaluated and compared to commercial PI. To demonstrate and evaluate the hybridized approach in a potential end-use application, the author also characterized the achievable microwave application performance of UV-DIW polyimide relative to the existing highest performance commercially available printed substrate material. The experiments in this thesis found an 83% and 66% decrease in resistivity from extrusion and AJ printed inks due to the ability of the printed PI to be processed at higher temperatures. Furthermore, UV-DIW PI was found to have similar dielectric properties to commercial PI film, which indicates that it can serve as a high-performance dielectric substrate. Finally, the high-temperature processing stability was able to decrease the performance gap in microwave application performance between the higher performing dielectric substrate, ULTEM 1010. These results show that UV-DIW could serve as a dielectric substrate for hybridized AM-DW electronic parts with higher performance and the ability to be deployed in harsher environments than previous AM-DW electronic parts explored in literature.

A methodology and prototype has been developed which enables users of GML and SCRIPT on an IBM 3090 to preview documents on a locally attached personal computer before printing. Currently, no utility exists to accomplish this activity. This new preview process is graphical in nature and provides an absolute picture of the document, exactly as it will be printed on an IBM 3812 laser printer. / Master of Science

The task of determining which of many available color-difference formulae is appropriate for any give application can be arduous. Researchers and practitioners alike are faced with the selection of one formula which best describes perceived color differences under conditions in which the equation is to be employed. The idea that one equation can be formulated which takes into consideration all factors affecting perceived color difference has yet to be realized, and perhaps never will. As a result, an “every man for himself” approach has developed. Yet, color-difference equations are continually being applied to conditions without empirical evidence to support their use. While the 1976 CIELAB Color Difference Equation has been applied for some time in the photographic industry, its use in describing the perceived magnitude of large color differences in photographic prints has not been validated. Furthermore, a good deal of research has suggested that the CIELAB equation is not applicable under numerous conditions of color-difference assessment. Nonetheless, the results of the study reported here support the use of CIELAB over four other formulae (CIELUV, CMC (1:1), Richter, and Yu’v’) for describing perceived color differences in photographic prints. CIELAB produced moderate correlations for both experienced and non-experienced color judges over the range of color space examined. The results of this work support the use of the 1976 CIELAB Color Difference Equation for describing the perceived magnitude of moderate and large color differences in photographic prints. / Master of Science