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The successful production of a wide range of polymer latex products relies on the ability to control the rates of particle nucleation, growth and coagulation in order to maintain control over the particle size distribution (PSD). The development of advanced population balance models (PBMs) has simplified this task at the laboratory scale, but commercialization remains challenging as it is difficult to maintain control over the composition (i.e. spatial distributions of reactant concentration) of larger reactors. The objective of this thesis is to develop and test a combined Computational Fluid Dynamics (CFD) -PBM hybrid modeling framework. This hybrid modeling framework can be used to study the impact of changes in process scale on product quality, as measured by the PSD. The modeling framework developed herein differs from previously-published frameworks in that it uses information computed from species tracking simulations to divide the reactor into a series of interconnected zones, thereby ensuring the reactor is zoned based on a mixing metric. Subsequently, an emulsion polymerization model is solved on this relatively course grid in order to determine the time evolution of the PSD. Examination of shear rate profiles generated using CFD simulation (at varying reactor scales) suggests that, dependent on conditions, mechanically-induced coagulation cannot be neglected at either the laboratory or the commercial scale. However, the coagulation models that are formulated to measure the contributions of both types of coagulation simultaneously are either computationally expensive or inaccurate. For this reason the decision was made to utilize a DLVO-coagulation model in the framework. The second part of the thesis focused on modeling the controlled coagulation of high solids content latexes. POLY3D, a CFD code designed to model the flow of non-Newtonian fluids, was modified to communicate directly with a multi-compartment PBM. The hybrid framework was shown to be well-suited for modeling the controlled coagulation of high solid content latexes in the laminar regime. It was found that changing the size of the reactor affected the latex PSD obtained at the end of the process. In the third part of the thesis, the framework was adapted to work with Fluent, a commercial CFD code, in order to investigate the scale-up of a styrene emulsion polymerization reaction under isothermal conditions. The simulation results indicated that the ability to maintain good control of the PSD was inversely related to the reactor blend time. While the framework must be adapted further in order to model a wider range of polymerization processes, the value of the framework, in obtaining information that would otherwise be unavailable, was demonstrated. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2012-05-01 07:09:08.362

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.

The direct catalytic hydrogenation of nitrile butadiene rubber (NBR) in latex form was studied as a model system for the development of a new latex hydrogenation process for the modification of unsaturated diene-based polymers. NBR is a synthetic rubber of copolymerized acrylonitrile and butadiene produced in latex form by emulsion polymerization. The catalytic hydrogenation of NBR is an important post-polymerization process resulting in a more stable and tougher derivative, hydrogenated NBR (HNBR), which has been widely used in the automotive and oil drilling industry. The present commercial process involves a number of cumbersome steps to obtain solid NBR from the latex and subsequent dissolution of the solid NBR in a large amount of organic solvent followed by solvent recovery after coagulation of the hydrogenated NBR. Since NBR is produced in latex form, it is very desirable to directly hydrogenate NBR in the latex form which will significantly simplify the hydrogenation process and facilitate subsequent applications. As an economical and environmentally benign alternative to the commercial processes based on the hydrogenation of NBR in organic solution, this direct latex hydrogenation process is of special interest to industry. The objective of this project is to develop an efficient catalytic system in order to realize the direct catalytic hydrogenation of NBR in latex form. OsHCl(CO)(O2)(PCy3)2 was initially used as the catalyst to investigate the possibility of hydrogenation of NBR in latex form and to understand the major factors which affect the hydrogenation operation. It was found that an organic solvent which is capable of dissolving or swelling the NBR was needed in a very small amount for the latex hydrogenation using the Os catalyst, and gel occurred in such a catalytic system during hydrogenation. Wilkinson’s catalyst, RhCl(PPh3)3, was then used for the latex hydrogenation in the presence of a small amount of solvent successfully without gel formation. Further investigation found that Wilkinson’s catalyst has a high activity for NBR latex hydrogenation without the use of any organic solvent. The influences of various operation conditions on hydrogenation rate, such as catalyst and polymer concentrations, latex system composition, agitation, reaction temperature and hydrogen pressure, have been investigated. It was found that the addition of triphenylphosphine (TPP) has a critical effect for the hydrogenation of NBR latex, and the hydrogenation rate was mainly controlled by the amount of catalyst which diffused into the polymer particles. In the presence of TPP, NBR latex can be hydrogenated to more than 95% degree of hydrogenation after about 30 hours at 160oC using Wilkinson’s catalyst with a catalyst to NBR rubber ratio of 1 wt%, without the addition of any organic solvent. The apparent activation energy for such NBR latex hydrogenation over the temperature range of 152oC to 170oC was found to be 57.0 kJ/mol. In the present study, it was also found that there are some impurities within the NBR latex which are detrimental to the hydrogenation reaction and are suspected to be water-soluble surfactant molecules. Deliberately designed solution hydrogenation experiments were conducted to study the impurity issue, and proper latex treatment methods have been found to purify the latex before hydrogenation. To improve the hydrogenation rate and to optimize the latex hydrogenation system, water soluble RhCl(TPPMS)3 catalyst (TPPMS: monosulphonated-triphenylphosphine) was used for the latex hydrogenation of NBR. The latex hydrogenation using the water soluble catalyst with TPP can achieve more than 90% degree of hydrogenation within 20 hours at 160oC. Further experiments using RhCl3 with TPP proved that the water soluble RhCl3 can be directly used as a catalyst precursor to generate the catalytic species in situ for the latex hydrogenation, and a stable NBR latex with 96% degree of hydrogenation can be produced without any gel problem within 19 hours of reaction at 160oC. The catalyst mass transport processes for these Rh based catalysts in the latex system were investigated in order to further optimize the solvent-free latex hydrogenation process. While maintaining the emulsified state of the original latex, the direct catalytic hydrogenation of NBR latex can be carried out efficiently without any cross-linking problem to more than 92% degree of hydrogenation within 8 hours at 160oC. As a result of this research project, new latex hydrogenation technologies were successfully developed to fulfill all major requirements for a solvent-free polymer latex hydrogenation route, which is a significant milestone for the improvement of this polymer modification technology. The finding of TPP’s role as the “catalyst mass transfer promoter” is a breakthrough for the research field related to the hydrogenation of unsaturated diene-based polymers in latex form.

The direct catalytic hydrogenation of nitrile butadiene rubber (NBR) in latex form was studied as a model system for the development of a new latex hydrogenation process for the modification of unsaturated diene-based polymers. NBR is a synthetic rubber of copolymerized acrylonitrile and butadiene produced in latex form by emulsion polymerization. The catalytic hydrogenation of NBR is an important post-polymerization process resulting in a more stable and tougher derivative, hydrogenated NBR (HNBR), which has been widely used in the automotive and oil drilling industry. The present commercial process involves a number of cumbersome steps to obtain solid NBR from the latex and subsequent dissolution of the solid NBR in a large amount of organic solvent followed by solvent recovery after coagulation of the hydrogenated NBR. Since NBR is produced in latex form, it is very desirable to directly hydrogenate NBR in the latex form which will significantly simplify the hydrogenation process and facilitate subsequent applications. As an economical and environmentally benign alternative to the commercial processes based on the hydrogenation of NBR in organic solution, this direct latex hydrogenation process is of special interest to industry. The objective of this project is to develop an efficient catalytic system in order to realize the direct catalytic hydrogenation of NBR in latex form. OsHCl(CO)(O2)(PCy3)2 was initially used as the catalyst to investigate the possibility of hydrogenation of NBR in latex form and to understand the major factors which affect the hydrogenation operation. It was found that an organic solvent which is capable of dissolving or swelling the NBR was needed in a very small amount for the latex hydrogenation using the Os catalyst, and gel occurred in such a catalytic system during hydrogenation. Wilkinson’s catalyst, RhCl(PPh3)3, was then used for the latex hydrogenation in the presence of a small amount of solvent successfully without gel formation. Further investigation found that Wilkinson’s catalyst has a high activity for NBR latex hydrogenation without the use of any organic solvent. The influences of various operation conditions on hydrogenation rate, such as catalyst and polymer concentrations, latex system composition, agitation, reaction temperature and hydrogen pressure, have been investigated. It was found that the addition of triphenylphosphine (TPP) has a critical effect for the hydrogenation of NBR latex, and the hydrogenation rate was mainly controlled by the amount of catalyst which diffused into the polymer particles. In the presence of TPP, NBR latex can be hydrogenated to more than 95% degree of hydrogenation after about 30 hours at 160oC using Wilkinson’s catalyst with a catalyst to NBR rubber ratio of 1 wt%, without the addition of any organic solvent. The apparent activation energy for such NBR latex hydrogenation over the temperature range of 152oC to 170oC was found to be 57.0 kJ/mol. In the present study, it was also found that there are some impurities within the NBR latex which are detrimental to the hydrogenation reaction and are suspected to be water-soluble surfactant molecules. Deliberately designed solution hydrogenation experiments were conducted to study the impurity issue, and proper latex treatment methods have been found to purify the latex before hydrogenation. To improve the hydrogenation rate and to optimize the latex hydrogenation system, water soluble RhCl(TPPMS)3 catalyst (TPPMS: monosulphonated-triphenylphosphine) was used for the latex hydrogenation of NBR. The latex hydrogenation using the water soluble catalyst with TPP can achieve more than 90% degree of hydrogenation within 20 hours at 160oC. Further experiments using RhCl3 with TPP proved that the water soluble RhCl3 can be directly used as a catalyst precursor to generate the catalytic species in situ for the latex hydrogenation, and a stable NBR latex with 96% degree of hydrogenation can be produced without any gel problem within 19 hours of reaction at 160oC. The catalyst mass transport processes for these Rh based catalysts in the latex system were investigated in order to further optimize the solvent-free latex hydrogenation process. While maintaining the emulsified state of the original latex, the direct catalytic hydrogenation of NBR latex can be carried out efficiently without any cross-linking problem to more than 92% degree of hydrogenation within 8 hours at 160oC. As a result of this research project, new latex hydrogenation technologies were successfully developed to fulfill all major requirements for a solvent-free polymer latex hydrogenation route, which is a significant milestone for the improvement of this polymer modification technology. The finding of TPP’s role as the “catalyst mass transfer promoter” is a breakthrough for the research field related to the hydrogenation of unsaturated diene-based polymers in latex form.

Yes / This study examines the feasibility of using colloidal silica nanoparticles as active agents in high concentration waterborne polymer latex formulations. We showed that distributing the silica throughout the waterborne emulsion formed a composite coating material with a hydrophilic surface that consequently reduced exterior dirt pickup. Two grades of silica nanoparticles were studied, one using sodium stabilisation and another using epoxysilane modification to introduce glycidox-ypropyltrimethoxysilane surface functionality. Rheological study of the waterborne latex on mixing showed that there was an immediate pH responsive interaction between the silica sols and the polymer latex. Once loading of sodium charge stabilised silica NPs exceeded the volume required for heteroflocculation to occur the mixture demonstrated the potential to gel on standing – a process which took weeks, or months, to occur depending on the pH and relative concentrations used. At least fifty percent silane modification to the NP surface was found to be necessary to maintain a stable colloidal dispersion for long term storage of the waterborne latex. Despite this both grades of silica were found to imbue reductions in dirt pickup when applied to exterior masonry concrete studies over a 3-month weathering test / This work was supported by the Royal Society of Chemistry [E21-8346952505].

Le séchage d’une solution chargée en particules est la solution la plus simple pour couvrir uniformément la surface d’un matériau. Le choix de la solution et ses propriétés physico-chimiques dictent alors le comportement du film obtenu. Le matériau peut ainsi être rendu hydrophobe en appliquant un tapis de molécules qui n’ont aucune affinité avec l’eau. Un moyen d’améliorer encore cette hydrophobie est de modeler la surface pour incorporer une certaine rugosité dans le revêtement. Cette stratégie est adoptée par plusieurs végétaux, dont le plus célèbre est le lotus.L’évaporation de suspensions apparait comme la méthode la plus simple pour parvenir à la structuration de la surface des matériaux. L’exemple le plus éloquent est celui de la goutte de café, où les particules viennent préférentiellement s’agglomérer sur son périmètre, portées par les différents flux résultant du mécanisme de séchage. Cependant, ce procédé d’auto-assemblage des particules sur la ligne triple air-liquide-substrat au cours du séchage, est difficile à appréhender. Ce constat est lié à la synergie entre la rhéologie des suspensions, leur physico-chimie et les aspects de tension inter faciale, qui s’opère au cours du procédé d’évaporation.Le travail proposé ici vise à comprendre et à maitriser le déplacement de la ligne triple pour accroitre le potentiel de cette méthode d’élaboration de revêtements. Nous proposons une méthode qui permet d’agir sur cette ligne triple. A la sortie de notre dispositif, le liquide est soumis à une évaporation libre, si bien que la ligne de contact adopte un mouvement périodique, apparenté à une respiration. Ce phénomène, peut être contrôlé en amplitude et en fréquence. Par la combinaison de paramètres mécaniques propres au procédé et d’autres intrinsèque au fluide, l’expérimentateur est capable de gouverner ce mouvement, ainsi que le profil du ménisque formé.La connaissance des moyens d’actions sur la respiration de la ligne triple est ensuite utilisée pour produire des surfaces périodiques. Ces dernières sont issues du séchage de latex de polymère. Le comportement cyclique de la ligne triple, combiné avec un déplacement contrôlé du substrat, permet de créer des zones préférentielles de dépôt. Les surfaces obtenues présentent un réseau de lignes successives, dont la longueur d’onde se rapporte aux paramètres du procédé. / Solvent evaporation appears as an easy way to deposit a periodic film on any surface. Its resulting structure is directly linked to the particles contained on the suspension and its behaviour with its solid and liquid environment during drying step. The coffee ring effect is the most eloquent example, which is characterized by a preferential agglomeration of the particle in the drop periphery. Such process is difficult to assess: handling the air-liquid-substrate interface movement is a basic need to increase the technical power of that coating method.To investigate the contact line motion during drying, we focus on the meniscus, which comes from a liquid flow between a sealed container and a substrate. Observations of liquid flowing out such disposal show a cyclic movement. Such phenomenon can be compared to a breathing of the contact line. The present work is firstly dedicated to the characterization of that periodic movement. These learnings are then applied to polymer latexes to produce periodic films.Our characterization method is based on meniscus observation and force balance recording. The observed breathing can be tuned in frequency and amplitude, by acting both on physical properties of the solvents, and geometrical settings of the device. Surface tension play a key role in the movement, by acting on the meniscus shape. Geometrical settings appears to affect the evaporation process. On a global scale, the rate is constant but the disposal gap is directly linked to the cycle frequency.Eventually, our disposal is used to coat smooth surface with polymer latexes. The self-organization of particles during the drying process is tried to be controlled by the periodic motion of the contact line. The roughness of the obtained textured coating is expected to be tuned by a combined choice of disposal settings and specific solutions properties.

In this thesis, the development of mechanical properties and structure of latex modified cementious materials during hydration was studied. Latex modified materials are composites of inorganic cement (portland cement) and organic polymer latex. Preparation, processing and fabrication of the polymer cement material based on portland cement was optimized with aim to reach the most compact structure of the product with the finest mechanical characters. The experimental part was pointed to observe influence of the type and amount of polymer latex with focus on mechanical characters and hydration kinetics with given filling as well as without it. In presented work, the possibility of compaction of the material by high-shear mixing within twin-roll mixer (the prototype for production of MDF composite) was verified. The second part of the labor was aimed to analysis of prepared polymer-cementitious material. For determination of influence of batching of added polymer latex on hydration of cement paste the thermal analysis (DTA/TGA) and infrared spectroscopy of composite was done. At last the microscopic observation by optical microscope was carried.