Since their invention in the 19th century, polymers have played an essential role, yet their full potential in biomedicine remains largely untapped. Biocompatible polymers, known for their flexibility, accessibility, and modifiability, hold promise in creating complex biomimetic structures for bioscaffolds and biosensors. 3D printing, an emerging manufacturing technique, enables on-demand production of intricate structures, offering significant potential for personalized medicine and advanced biomedical engineering. This thesis focuses on designing and developing polymer-based bioscaffolds and biosensors using 3D printing. Chapter 1 provides an all-round introduction to common 3D printing techniques and polymeric biomaterials, especially biodegradable polymers. In Chapter 2, a gill-mimicking thermoelectric generator (TEG) was created to harvest body temperature and monitor bio-signals without external power. The out-of-plane geometry is obtained with fused deposition modeling (FDM), which is crucial for effective contact with various curved surfaces. Further improvements in biocompatibility enable the material to be implanted in vivo. Chapter 3 discusses UV-facilitated DIW printing for pelvic organ prolapse (POP) tissue scaffolds, featuring crosslink strategies for native tissue-like mechanical behavior. The double network comprises thiol-ene UV-initiated chemical bonds and alkaline-induced crystal regions as physical crosslink nodes. The crosslink density affects the degradation rate of the scaffold, enabling a slow degradation behavior beneficial to the recovery of the injured tissue. Chapter 4 presents a novel artificial artery design with varying moduli and natural polymers for bypass surgeries. The inner and outer layers of the conduit were stretched successively under different strains, endowing the vessel with varying moduli. Natural polymers were utilized to achieve low cytotoxicity and promote adequate cell adhesion. Additionally, the gelation behavior and the ink composition suitable for extrusion with a DIW platform were thoroughly studied. Image analysis, finite element analysis, and machine learning were employed to substantiate the findings regarding mechanical properties, extrusion quality, and printing fidelity in Chapters 3 and 4. This combination of computer-assisted analysis with experimental results enhances the robustness of the studies. Lastly, Chapter 5 provides an outlook and perspectives on the applications of biocompatible polymeric materials manufactured by 3D printing in the field of health applications.

Additive manufacturing, also known as 3D printing, has revolutionized modern manufacturing in several key areas: complex geometry fabrication, rapid prototyping and iteration, customization and personalization, reduced material waste, supply chain flexibility, complex assemblies and consolidated parts, and material innovation. As the technology continues to evolve, its impact on manufacturing is expected to grow, driving further innovation and reshaping traditional production processes. Some innovation examples in this field are inspired by natural or bio-systems, such as honeycomb structures for internal morphological control to increase strength, bio-mimetic composites for scaffold structures, or shape memory materials in 4D printing for targeted drug delivery. However, the technology is limited by its ability to manipulate multiple materials, especially tuning their submicron characteristics when they show non-compatible chemical or physical features. For example, the deposition and patterning of nanoparticles with different dimensions have seen little success, except in highly precise and slow 3D printing processes like aerojet or electrohydrodynamic. Taking inspiration from the layered patterns and structures found in nature, this research aims to demonstrate the development and versatility of a newly developed ink-based composite 3D printing mechanism called multiphase direct ink writing (MDIW). The MDIW is a multi-materials extrusion system, with a unique nozzle design that can accommodate two immiscible and non-compatible polymer or nano-composite solutions as feedstock. The intricate internal structure of the nozzle enables the rearrangement of the feedstock in alternating layers (i.e., ABAB...) and multiplied within each printed line. This research will first highlight the design and development of the MDIW 3D printing mechanism, followed by laminate processing to establish the requirements of layer formation in the XY-axis and the effect of layer formation on its microstructural and mechanical properties. Next, the versatility of the mechanism is also shown through the one-step fabrication of shape memory polymers with dual stimuli responsiveness, highlighting the 4D printing capabilities. Moreover, the MDIW's capability of dual nanoparticle patterning for manufacturing multi-functional carbon-carbon composites will be highlighted. Comprehensive and in-depth studies are conducted to investigate the morphology-structure-property relationships, demonstrating potential applications in structural engineering, smart and intelligent devices, miniature robotics, and high-temperature systems.

For the past two centuries, coal has played a vital role as the primary carbon source, fueling industries and enabling the production of essential carbon-rich materials, including carbon nanotubes, graphite, and diamond. However, the global transition towards sustainable energy production has resulted in a decline in coal usage for energy purposes, with the United States alone witnessing a substantial 50% reduction over the past decade. This shift aligns with the UN’s 2030 sustainability goals, which emphasize the reduction of greenhouse gas emissions and the promotion of cleaner energy sources. Despite the decreased use in energy production, the abundance of coal has sparked interest in exploring its potential for other sustainable and valuable applications.In this context, Direct Ink Writing (DIW) has emerged as a promising additive manufacturing technique that employs liquid or gel-like resins to construct three-dimensional structures. DIW offers a unique advantage by allowing the incorporation of particulate reinforcements, which enhance the properties and functionalities of the materials. This study focuses on evaluating the viability of coal as a sustainable and cost-effective substitute for other carbon-based reinforcements, such as graphite or carbon nanotubes. The research utilizes a thermosetting resin based on phenol-formaldehyde (commercially known as Bakelite) as the matrix, while pulverized coal (250 µm) and carbon black (CB) function as the reinforcements. The DIW ink is meticulously formulated to exhibit shear-thinning behavior, facilitating uniform and continuous printing of structures. Mechanical property testing of the printed structures was conducted following ASTM standards. Interestingly, the study reveals that incorporating a 2 wt% concentration of coal in the resin yields the most significant improvements in tensile modulus and flexural strength, with enhancements of 35% and 12.5% respectively. These findings underscore the promising potential of coal as a sustainable and environmentally friendly reinforcement material in additive manufacturing applications. By harnessing the unique properties of coal, this research opens new avenues for its utilization in the pursuit of greener and more efficient manufacturing processes.

Nanoparticle (NP) assembly is critical where NPs are organized into complex superstructures through direct and indirect interactions. Long-range NP orders have nanoscale locational selectivity, orientational alignment, and scalable micropatterning, which are indispensable for enabling multiple functionalities and improving the performances of different systems. Though nanoparticles can self-assemble into organized nanostructures via simple drying thermodynamics, scalability has been a primary issue. Thus, this research focuses on more scalable manufacturing for directed NP assembly. First, 3D printing was used for template fabrications with varying topology features. Next, nanoparticle engineering with colloidal and surface studies leads to desirable NP packing on template surfaces. Finally, the processed devices will also demonstrate a few applications of surface micropatterning with nanoscale particle orders. Specifically, a few manufacturing procedures involve (i) stereolithography (SLA)/layer-by-layer dip coating, (ii) continuous liquid interface projection (CLIP)/ink writing, (iii) fused deposition melting (FDM)/direct ink writing, and (iv) multiphase direct ink writing (MDIW)/wet etching. To demonstrate the applicability of hybrid manufacturing, a broad range of nanoparticles, including carbon nanofibers (CNFs), MXene nanoflakes, and boron nitride nanoplatelets (BNNPs) were studied in this research. With well-managed template physics and NP dispersion control, nanoparticle orientational alignment and positional preferences are driven by short- and long-range intermolecular interactions (e.g., convective, van der Waals, capillarity, shear, and other secondary bonding). The printed devices displayed multifunctional properties, i.e., anisotropic conductivity, piezoresistive and chemical sensitivity, mechanical durability, and heat dissipation capabilities, for microelectronic applications. This fabrication technique shows enormous potential for rapid, scalable, and low-cost manufacturing of hierarchical structures, especially for micropatterning of nanoparticles not easily accessible through conventional processing methods.

Nanomaterials redefine the lens through which the world is viewed today. The miniaturization of devices and systems to the nanoscale explodes the realm of what is possible as the interactions with neighboring atoms and molecules increase. This interactivity creates ripple effects that lead to superior mechanical, thermal, electrical, and optical properties that are highly desired across several industries. Two-dimensional (2D) materials are a branch of this family, and the focus of this paper revolves around a recent addition to this category called MXenes. The versatile properties of these 2D nanomaterials have made them unique, as they have the desired performance that can be utilized in several industries, especially energy management, wastewater treatment, and microelectronic devices. Followed by the MAX phase synthesis, hydrofluoric (HF) acid has been the primary etchant utilized to derive these 2D nanoparticles. However, alternative etchants via reactions are desirable to achieve similar selective etching without involving highly toxic HF. Therefore, this study investigated MXene synthesis and applications in 3D printing, followed by the formation of the precursor MAX, an optimized in-situ etching method, and streamlined post-etching processes to maximize 2D MXene yield. The etched powders were then analyzed using scanning electron microscopy (SEM), x-ray diffraction (XRD), atomic force microscopy (AFM), and energy-dispersive x-ray spectroscopy (EDS) characterization methods to verify and validate the MXene dimensions, chemistry, and crystal structures. Simple applications, such as the dispersion feasibility for customizing micropatterns via 3D printing, were also demonstrated as examples. Finally, this research showed the simple processing of 2D MXenes and their potential in structural support, heat dissipation, microelectronics, optical meta-surfaces, and other areas.

Progressive miniaturization in electronics demands advanced materials with excellent energy conversion and transport properties. Opportunities exist in novel material morphologies such as hierarchical structures, multi-functional composites and nanoscale architectures which may offer mechanical, thermal and electronic properties tailored to a wide range of applications (e.g., aerospace, robotics, biomedical etc.). However, the manufacturing capabilities have always posed a grand challenge in realizing the advanced material morphologies. Furthermore, the multi-scale modeling of complex material architectures has been extremely challenging owing to the limitations in computation methodologies and lack of understanding in nano-/micro-meter scale physics. To address these challenges, this work considers the morphology effect on carbon nanotube (CNT)-based composites, CNT fibers and thermoelectric (TE) materials. First, this work reports additively manufacturable TE morphologies and analyzes the thermo-electric transport behavior. This research introduces innovative honeycomb TE architectures that showed ~26% efficiency increase and ~25% density reduction compared to conventional rectangular TE architectures. Moreover, this work presents 3D printable compositionally segmented TE architecture which provides record-high efficiencies (up to 8.7%) over wide temperature ranges if the composition and aspect ratio of multiple TE materials are optimized within a single TE device. Next, this research proposes computationally efficient two-dimensional (2D) finite element model (FEM) to study the electrical and thermal properties in CNT based composites by simultaneously considering the stochastic CNT distributions, CNT fractions (upto 80%) and interfacial resistances. The FEM allows to estimate the theoretical maximum possible conductivities with corresponding interfacial resistances if the CNT morphologies are carefully controlled, along with appreciable insight into the energy transport physics. Then, this work proposes a data-driven surrogate model based on convolutional neural networks to rapidly approximate the composite conductivities in a second with accuracy > 98%, compared to FEM taking >100 minutes per simulation. Finally, this research presents a pseudo 2D FEM to approximate the electrical and thermal properties in CNT fibers at various CNT aspect ratios (up to 10,000) by simultaneously considering CNT-CNT interfacial effects along with the stochastic distribution of inter-bundle voids.

Pelvic organ prolapse (POP) is a condition involving the weakening of the pelvic floor, with a prevalence of up to 50% of women experiencing the condition to some degree. Individuals with the condition are susceptible to multiple symptoms include vaginal protrusion, dyspareunia, and difficulties with waste excretion. Risk factors are common and numerous for POP, and the economic burden of the condition poses a significant cost to nations worldwide. For many years, the primary solution to POP was the usage of transvaginal meshes, often composed of polypropylene, but rising reports of harmful side effects have led to their recall. Due to this, the space is open for novel solutions, and treatments based in regenerative medicine are on the rise. One such potential treatment is the usage of functionalized polyvinyl alcohol scaffolds to support the regeneration and strengthening of the pelvic floor. To validate the usage of this scaffold, this study focuses on the biocompatibility of the scaffolds, with specific focus on the maintenance of cell viability and proliferation on the scaffold. Through usage of metabolic assays and fluorescence microscopy, scaffolds composed of functional polyvinyl alcohol with cellulose have shown promise in supporting the cell types necessary for reconstructing the pelvic floor.

Pelvic organ prolapse (POP) is a condition involving the weakening of the pelvic floor, with a prevalence of up to 50% of women experiencing the condition to some degree. Individuals with the condition are susceptible to multiple symptoms include vaginal protrusion, dyspareunia, and difficulties with waste excretion. Risk factors are common and numerous for POP, and the economic burden of the condition poses a significant cost to nations worldwide. For many years, the primary solution to POP was the usage of transvaginal meshes, often composed of polypropylene, but rising reports of harmful side effects have led to their recall. Due to this, the space is open for novel solutions, and treatments based in regenerative medicine are on the rise. One such potential treatment is the usage of functionalized polyvinyl alcohol scaffolds to support the regeneration and strengthening of the pelvic floor. To validate the usage of this scaffold, this study focuses on the biocompatibility of the scaffolds, with specific focus on the maintenance of cell viability and proliferation on the scaffold. Through usage of metabolic assays and fluorescence microscopy, scaffolds composed of functional polyvinyl alcohol with cellulose have shown promise in supporting the cell types necessary for reconstructing the pelvic floor.

This dissertation is focused on the rheology scaling of metal particle reinforced polymermatrix composite made of solid and nanoporous metal powders to enable their continuous 3D printing at high (>60vol%) metal content. There remained a specific knowledge gap on how to predict successful extrusion with densely packed metals by utilizing their suspension melt rheological properties. In the first project, the scaling of the dynamic viscosity of melt-extrudate filaments made of Polylactic acid (PLA) and gas-atomized solid NiCu powders was studied as a function of the metal’s volumetric packing and feedstock pre-mixing strategies and correlated to its extrudability performance, which fitted well with the Krieger-Dougherty analytical model. 63.4 vol% Filaments were produced by employing solution-mixing strategy to reduce sintered part porosity and shrinkage. After sintering, the linear shrinkage dropped by 76% compared to the physical mixing. By characterizing metal particle reinforced polymer matrix composite feedstock via flow-sweep rheology, a distinct extension of shear-thinning towards high shear rates (i.e. 100 s-1) was observed at high metal content – a result that was attributed to the improved wall adhesion. In comparison, physically mixed filament failed to sustain more than 10s-1 shear rate proving that they were prone to wall slippage at a higher shear rate, giving an insight into the onset of extrusion jamming. In the second project, nanoporous copper made out of electroless chemical dealloying was utilized as fillers, because of their unique physiochemical properties. The role of capillary imbibition of polymers into metal nanopores was investigated to understand their effect on density, zero-shear viscosity, and shear thinning. It was observed that, although the polymeric fluid’s transient concentration regulates its wettability, the polymer chain length ultimately dictates its melt rheology, which consequentially facilitates densification of pores during vacuum annealing. Finally, it was demonstrated that higher imbibition into nanopores leads to extrusion failure due to a combined effect of volumetric packing increase and nanoconfinement, providing a deterministic materials design tool to enable continuous 3D printing. The outcome of this study might be beneficial to integrate nanoporous metals into binder-based 3D printing technology to fabricate interdigitated battery electrodes and multifunctional 3D printed electronics.