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.

Active colloids are small particles that can convert external energy supply into self-propulsion. Because of the existence of the energy current inside and across the system, active colloids exhibit behaviors that are far away from thermodynamic equilibrium. During the past decades, active colloids have been used to provide models for many different non-equilibrium system studies and have been designed to complete tasks on small scale. By tuning the particle size, shape, etc, or changing the actuation methods of the active colloid systems, people have developed a large number of different active colloid systems. Among all active colloid systems, the Quincke rotation system can effectively propel particles with rapid speed. This phenomenon refers to the spontaneous rolling of a dielectric sphere in a weakly conducting liquid under a DC electric field. Although the basic mechanism of a single Quincke roller has been well explained, some behaviors that occur in complex environments or with multiple Quincke particles are still mysteries. For example, one particle will move back and forth on the bottom electrode under a high electric DC field. This so-called Quincke Oscillation motion cannot be explained by the previous models well. So a new model is required. In this dissertation, we will focus on explaining this newly-discovered dynamic in the Quincke system. Then we will study the collective dynamics of multiple Quincke oscillators with designed experiments and models. In Chapter 1, the background and different actuation methods of active colloid systems are first introduced. Then the Quincke rotation system and its field-dependent dynamics are explained with a classic leaky dielectric model. The recent research results with Quincke systems are shortly reviewed afterward. In Chapter 2, we introduce the experimentally discovered Quincke Oscillation phenomenon. Then we reveal its dependency on liquid conductivity and particle size. This dynamic is finally explained by the asymmetric charging of the particle surface in the field-induced boundary layer near the electrode. This work opens the door to the study of the collective dynamics of Quincke oscillators. In Chapter 3, we first introduce a dynamical model considering the charge, dipole, and quadrupole moments of the sphere and predict its oscillatory motion under a non-uniform liquid conductivity environment. Then we study the behavior of two coupled Quincke oscillators with far-field hydrodynamic and electrostatic interactions. The numerical simulations predict the synchronization and alignment of two oscillators with fixed positions. We further develop a model based on weakly coupled oscillator assumptions by considering the relative phase and oscillating orientations of two oscillators. The model successfully explains the numerical simulation results and can be applied to other active colloid systems with multiple mobile oscillators. In Chapter 4, we show that the Quincke oscillators can assemble into a cluster and oscillate with high synchronization and alignment. This formation of the cluster can also increase the oscillation frequency of the oscillators. By considering the perfect contact rolling of the oscillators on the electrode, we develop a weakly coupled oscillator theory model. This model explains the tendency of particles to synchronize and align in a cluster and predicts the increase of the oscillation frequency when particles are in synchronized phases. The cluster is stabilized due to the existing phase waves observed in experiments and simulations. In Chapter 5, we introduce two other studies on Quincke rollers with different experimental designs. Particles of helical shape exhibit self-propulsion in the liquid bulk and highlight the role of shape in controlling particle dynamics. For multiple spheres in a height-confined system, the particles display a transition from a fluctuating state to an absorbing stable state depending on their density and the applied field strength. This work provides an experimental model for studying absorbing state. In Chapter 6, the development of the Quincke system study is reviewed and some future directions are suggested.

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This dissertation explores the intersection between the fields of colloid science and statistical inference where the stochastic trajectories of colloidal particles are captured by video microscopy, reconstructed using particle tracking algorithms, and analyzed using physics-based models and probabilistic programming techniques. Although these two fields may initially seem disparate, the dynamics of micro- and nano-sized particles dispersed in liquids at room temperature are inherently stochastic due to Brownian motion. Further, both the particles under observation and their environment are heterogeneous, leading to variability between particles as well. We use Bayesian data analysis to infer the uncertain parameters of physics-based models that describe the observed trajectories, explicitly modeling the hierarchical structure of the noise under a set of varying experimental conditions. We set the stage in Chapter 1 by introducing Robert Brown's curious observation of incessantly diffusing pollen grains and Albert Einstein's statistical physics model that describes their motion. We analyze Jean Baptiste Perrin's data from Les Atomes using a probabilistic model to infer the uncertain diffusivities of the colloids. We show how the Bayesian paradigm allows us to assign and update our credences, before and after observing this data and quantify the information gained by the observation. In Chapter 2, we build on these concepts to provide insight on the phenomenon of enhanced enzyme diffusion, whereby enzymes are purported to diffuse faster in the presence of their substrate. We develop a hierarchical model of enzyme diffusion that describes the stochastic dynamics of individual enzymes drawn from a dispersed population. Using this model, we analyze single molecule imaging data of urease enzymes to infer their uncertain diffusivities for different substrate concentrations. Our analysis emphasizes the important role of model criticism for establishing self-consistency between experimental observations and model predictions; moreover, we caution against drawing strong conclusions when such consistency cannot be established. In Chapter 3, we automate, and optimize the data acquisition process, tuning a resonant acoustic cell using minimal experimental resources. By iterating a cycle of observation, inference, and design, we select the frequency the applied signal and the framerate of the data acquisition, garnering the same amount of information as a grid search approach with a fraction of the data. Finally, in Chapter 4, we discuss the role of Bayesian inference and design to optimize functional goals and discuss selected examples on where black-box techniques may prove useful. We review the current state of the art for magnetically actuated colloids and pose the search for autonomous magnetic behaviors as a design problem, offering insight as we seek to augment and accelerate the capabilities of micron scale magnetically actuated colloids using modern computational techniques.

The presence of biologically-active estrogenic endocrine disrupting compounds (EDCs) in treated effluents from biological wastewater treatment facilities has prompted wide-spread interest in the behavior of these contaminants during the activated sludge process. The yeast-estrogen screen (YES) was used to quantify the estrogenic activity of samples taken from different areas of three wastewater treatment facilities. An estrogenic mass-balance around these facilities revealed that the majority of influent estrogenic activity was removed in the activated sludge process, but the main route for EDC discharge to the natural environment was via the treated effluent. The estrogenic activity in the effluent from a membrane bioreactor (MBR) was lower compared to a fully aerobic activated sludge process using secondary clarification, suggesting that enhanced removal of particulate and colloidal material may improve EDC removal efficiency. Colloidal material was obtained from settled mixed liquor suspended solids (MLSS) collected from a pilot MBR and a full-scale activated sludge process that included anoxic and aerobic zones. The MLSS was sized fractionated by filtration, and used to quantify the sorption coefficients for pyrene, 17&#946;-estradiol (E2), and 17α-ethinylestradiol (EE2) by fluorescence quenching. The MLSS-derived colloidal organic carbon (COC) sorption coefficient (Kcoc) for pyrene ranged from (< 1 to 80) L/kgcoc, indicating a similar affinity for pyrene compared to natural organic matter. Kcoc coefficients for E2 ranged between (< 1 to 158) L/kgcoc for E2 and (< 1 to 228) L/kgcoc for EE2, and are the highest E2 and EE2 sorption coefficients reported in the literature to date. There was a strong correlation between the Kcoc coefficients and molar extinction coefficient at 280 nm (e280) for pyrene and E2, suggesting that the interaction of the π;-electrons is an important factor in determining overall sorption behavior. There was no such correlation for EE2. Based on the Kcoc coefficients and COC concentrations of the samples, between 1 and 50% of the aqueous E2 and EE2 concentrations were associated with colloidal material. In a novel application of the YES bioassay, the bioavailability of colloid-associated E2 was quantified by comparing the EC50 values of the dose-response curves generated in the presence and absence of size fractionated COC. An increase in EC50 values as a function of COC concentration was attributed to a reduction in bioavailability of E2, suggesting that MLSS-derived COC can reduce, but not eliminate, the biological impact of EDCs. However, there was a high degree of variability in the EC50 values, and estimates of the colloid-associated E2 fraction based on the Kcoc-e280 correlation were unsuccessful in accurately predicting increases in EC50 values. Nevertheless, the YES bioassay may represent a powerful tool in determining the bioavailability of EDCs in complex environmental samples. Results from this research effort suggest that the colloidal phase derived from activated sludge systems represents an important transport vehicle whereby EDCs and other trace organic compounds can enter into the natural environment. Consequently, wastewater treatment plants discharging to sensitive ecosystems or involved with direct water reuse programs should optimize the treatment process to remove colloidal material. / Ph. D.

The knowledge of particle size and size distribution are important parameters for understanding the behavior of numerous colloid systems. These areas include for example, clays, viruses, paints and blood. Until recently this information could be obtained only by the use of expensive, slow and complex instrumentation. Hydrodynamic chromatography provides a means of investigating particles in the submicron and micron region. The separation mechanism of this method is based upon the flow parameters with which the solute particles interact as they pass through a packed column. In the past the interpretation of these chromatograms has been based upon the mathematical modeling of the column parameters. We have developed a new multiwavelength detector system to be used in conjunction with hydrodynamic chromatography which provides size and concentration information of the eluant directly. The result is a rugged system that provides size and size distribution information rapidly and at low cost. / Ph. D.

Unicellular algae have proven to be extremely difficult to separate from their liquid environment, and at the present time no economical process exists. A novel technique using colloidal gas aphrons (CGA) has been investigated for harvesting <i>Chlorella vulgaris</i>, a green algae, from dilute suspension. CGA dispersions consist of very small gas bubbles, on the order of 25 microns in diameter, that are each encapsulated in an aqueous shell of surfactant solution. The process is based on the technology of CGA flotation, which involves the formation of algae-bubble complexes (possibly including dissolved inorganic ions) and their subsequent flotation into a stable froth at the surface. At neutral pH, the efficiency of algae removal was maximized when a cationic surfactant (lauryl pyridinium chloride) was used for CGA generation. At pH 10, both the cationic and anionic (sodium dodecyl benzene sulfonate> CGA dispersions yielded comparable removals. Addition of small quantities of alum (to 10^-4 M) improved removals using the cationic CGA, and at pH 10 this combination yielded the maximum removals that were achieved: 52.1% removal after a single application of CGA dispersion (1 to 1, dispersion to sample volume ratio), and 89.2% removal after an additional application. Although the of CGA-flotation has yet to be determined, it is proposed that the process occurs through the interaction of the CGA bubbles, the algal cells, and possibly dissolved ions to form buoyant flocs. / M.S.

This thesis describes direct measurements of equilibrium adsorption of ions in thin (< 100 nm) aqueous films. Adsorption in thin films is important because it is through adsorption that the stability of colloidal suspensions is frequently tuned. The vast majority of measurements of adsorption to date have been to a single interfaces, whereas the subject of this thesis is adsorption in a thin film between two interfaces. There are two isolated interfaces when particles in a suspension are far apart, but during the collision, a thin film forms between the particles, and the properties of the thin film determines the stability of the colloid. Thus, adsorption in the thin film determines the stability of the colloidal dispersion. There is a distinct gap in the scientific literature concerning adsorption in thin films mainly because there is no technique for measuring such adsorption. To fill this gap in knowledge, I first developed of a technique to directly measure adsorption in thin films, and then applied this technique to explore the behavior of co-ions near charged interfaces as a function of bulk solution composition and the thickness of the film. The adsorption behavior of fluorescein, a di-anion, to negatively charged silica interfaces was studied in dilute electrolytes. The focus was on the effect of the electrostatic screening length, or Debye-length. The separation was measured using interference microscopy and the adsorption of fluorescein was measured using fluorescence microscopy. The Debye-length was altered by variation of the background salt (NaCl) concentration in dilute (<1 M) solution. The surface excess of adsorption for fluorescein was shown to depend on both the Debye-length and the separation distance between two interfaces. Increasing the Debye-length from 4 nm to 21 nm increased the plateau surface excess at large separations, and decreasing the separation lead to a monotonically decreasing surface excess. The surface excess varied over a range that scaled with the Debye-length. The results were compared to solution of the Poisson-Boltzmann model and good agreement was found between the model and the experiment. The effect of background salt concentration on fluorescein adsorption was also studied in concentrated electrolytes (2.5 – 10 M) for various monovalent salts (LiCl, NaCl and CsCl). The results showed that the fitted electrostatic screening length showed an opposite trend to predictions from Poisson-Boltzmann, with the screening-length increasing with increasing salt concentration. That is, the Debye-length prediction was quantitatively incorrect and predicts the incorrect trend. For example, in 10 M LiCl where the Debye-length is 0.1 nm, and therefore colloidal chemists would traditionally predict that double-layer forces are negligible, my results show that the actual decay length is about 10 nm, which is about the same as in 10-3 M LiCl solution. The rate of increase of screening-length as a function of concentration was also an ion specific effect. In addition, the results show that there is an inversion of the surface charge in concentrated salt solution. The original device on which all the above measurements were made had two limitations: (1) the maximum film thickness was 50 nm and (2) the film was asymmetric, which hampered calculation of the surface excess and increased the number of degrees of freedom in modeling of the adsorption. In the last part of my thesis, I describe development of a symmetric sample which (1) enables measurement of films up to 1 µm, (2) simplifies modeling of the optics by eliminating optical interference of the fluorescence excitation, and reduces the number of parameters when comparing to models. / Doctor of Philosophy / This thesis aims to understand the behavior of electrically charged molecules and atoms in thin nanometer scale (< 100 nm) liquid films subject to confinement between two charged interfaces. This situation frequently arises in colloidal suspensions, which consist of tiny sub-microscopic particles (colloid), droplets and large molecules dispersed in a second continuous medium. The stability of these suspensions, i.e. whether the colloidal materials agglomerate and sediment out of the suspension or remain stably suspended, depends on the surface forces between their interfaces during collision events, which frequently arise due to Brownian motion. As the fluid between particles thins as they approach each other during these collision events, the behavior of the dissolved molecules can be significantly different than when they are far apart due to the presence two interacting interfaces. Typically the dissolved molecules are used to tune the surface forces and understanding their behavior in confinement is relevant to a colloid scientist whose aim is to tune the behavior of the suspension. In the first part of this work, a technique is developed that serves as the static analogue to colloidal objects colliding with each other. The equilibrium behavior of a negatively charged fluorescent ion is measured as a function of film thickness and background salt concentration between two negatively charged interfaces. The Poisson-Boltzmann model predicts that with decreased salt concentration, there is a greater magnitude of depletion of the fluorescent ion at large separations and the characteristic length over which there is a change in the magnitude of depletion increases. Good agreement is found between the model and the experiment validating the technique developed and providing the first direct observation of molecular behavior subject to confinement as a function of solution composition. This effect of background salt type and concentration was tested for concentrated electrolytes as well. The experimental results showed an opposite trend to predictions from the Poisson-Boltzmann model. The fluorescent ion was now adsorbed to negatively charged interfaces indicating that the negatively charged interfaces were now positively charged. The magnitude of adsorption at large separations and characteristic length over which the magnitude of adsorption changes was a function of the salt concentration and the ion type. Finally, improvements were made to the original device to overcome limitations with the original device. The limitations were that (1) the maximum film thickness was 50 nm and (2) the interfaces were asymmetric which complicated theoretical calculations of the equilibrium behavior of the ions. In the last part of my thesis, I develop a sample which (1) enables measurements of films up to 1 µm and (2) simplifies the optical modeling necessary in the first two sections of this thesis.

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