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The development of algorithms for the automatic creation of finite element meshes composed entirely of hexahedra (all-hex) is an active area of research. All-hex meshes are desirable for their characteristic of high accuracy with a low node count. Sweeping is one of the most widely used algorithms for generating all-hex meshes. A limitation of sweeping, however, is that it can currently be applied only to prismatic or extruded geometry types. This thesis develops a method to combine sweeping with another algorithm known as "Grafting". Grafting adjusts the mesh on one volume to conform to a second volume. In this manner it is useful for meshing multi-axis geometry in that a single axis can be meshed with sweeping and then secondary axes can be grafted on. By creating an algorithm for automatically performing these processes, the base set of geometry that can be automatically meshed with these methods is greatly increased. This new algorithm is called Graft-Sweeping. With the combination of sweeping and Grafting, geometry that contains multiple source surfaces, multiple target surfaces, and multiple sweep axes can be meshed. The results of this algorithm on several example geometries are given showing the strengths and weaknesses of this technique. From the results it can be seen that the Graft-Sweep algorithm can produce a finite element mesh in about half the time of manual Grafting and sweeping operations with similar mesh quality. When compared to sweeping alone, Graft-Sweeping is several times faster but the quality is usually reduced. A second area of research for this thesis is to determine when Grafting can be used to enhance the meshing process. It is shown that the best results are obtained when Grafting is used on structured meshes and the mesh size is considerably smaller than the size of the feature that is being grafted.

<p> Swellable microspheres prepared by the precipitation polymerisation of divinylbenzene-80 (DVB-80) and 2-hydroxyethyl methacrylate (HEMA), in a solvent mixture of methyl ethyl ketone (MEK) and heptane, were functionalised with 2bromopropionyl bromide, and 2-bromoisobutyryl bromide to prepare Atom Transfer Radical Polymerisation (ATRP) initiators. </p> <p> Methyl acrylate (MA) and methyl methacrylate (MMA) were grafted from the microspheres using CuBr and either 4,4'-dinonyl-2,2'-dipyridyl (dNbipy), or N,N,N',N",N"-pentamethyldiethylenetriamine (PMDET A) ligands. The morphology of the grafted microspheres was studied using electron microscopy (ESEM and TEM) and x-ray microspectroscopy. Adding equimolar sacrificial initiator resulted in improved control over the grafting and gave grafted and soluble polymer, with narrow polydispersity (PDI) and number average molecular weight (Mn) close to expected values. </p> <p> Base catalysed transesterification was used to cleave the grafted polymer. It was found that adding free initiator permits grafting from within lightly cross-linked gels to be carried out with good control over Mn and PDI. </p> / Thesis / Master of Science (MSc)

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The objective of this thesis is to incorporate cellulose nanocrystals (CNCs) into polymer latexes prepared using various emulsion polymerization methods. CNCs are a promising new class of renewable materials with unique properties including nanoscale dimensions, a high aspect ratio, low density, and high strength. They show significant promise to enhance the properties of existing materials, but challenges often arise due to incompatibility and processing difficulties. This work investigates novel surface modification routes to improve the compatibility of CNCs with emulsion polymerization components, and aims to control the location and function of CNCs in latex systems in order to modify latex properties. Three approaches to incorporate CNCs into polymer latexes are presented: (1) exploiting CNC-surfactant interactions in order to promote CNCs as Pickering stabilizers or as “passive” additives in the water phase, (2) enhancing the surface activity of CNCs by adsorbing the surface active biopolymer methyl cellulose (MC) to act as Pickering co-stabilizers, or (3) hydrophobic modification of CNCs through polymer grafting in order to provide improved compatibility between CNCs and the monomer/polymer phase to incorporate CNCs into the latex core. First, the interactions between CNCs and surfactants were studied in suspension and at surfaces and the CNC-surfactant combinations were used to stabilize miniemulsion polymerization of methyl methacrylate (MMA), a model system used in this work. Oppositely charged CNCs and surfactants showed improved stability as Pickering stabilizers and the ability to co-stabilize the monomer/polymer-water interface. When like-charged CNCs and surfactants were used, the poly(methyl methacrylate) (PMMA) polymer particles were stabilized by surfactant only, while the CNCs remained in the water phase. Next, in order to avoid the use of surfactants, CNCs were coated with MC to provide improved surface activity. MC-coated CNCs were effectively used as Pickering stabilizers in the microsuspension polymerization of MMA, where a double morphology of PMMA particles was observed, and the morphology could be tuned based on the ratio of CNC to MC used. Finally, CNCs were modified with hydrophobic polymer via two different “grafting from” methods: free radical polymerization and atom transfer radical polymerization (ATRP). Free radical polymer grafting from CNCs resulted in polymer-grafted CNCs but the method lacked control over polymer graft length and graft density. To overcome this, CNCs were modified via surface initiated ATRP where considerably higher amounts of polymer were grafted from the CNCs in short reaction times and with simple purification steps. Furthermore, polymer-grafted CNCs were added to the monomer phase of the miniemulsion polymerization of MMA and latexes with CNCs inside the hydrophobic polymer particle core were prepared. Given the difficulties in characterizing polymer grafted CNCs, a novel solution state NMR method was used, whereby the modified CNCs were dissolved in ionic liquids and the polymer grafts were cleaved and collected to determine graft length and graft density. Overall, this work provides three approaches for the preparation of nanocomposite latexes with CNCs using PMMA as a model system. The results presented here may expand the use of CNCs in latex products such as adhesives, paints, coatings, and cosmetics. / Thesis / Doctor of Philosophy (PhD) / This research aims to prepare polymer latexes with tailorable properties using renewably-sourced particles and nanotechnology. Latexes are polymer particles dispersed in water, typically on the order of a few hundred to thousand nanometers (where a “nanometer” is one billionth of a meter), and are used in products such as adhesives, paints, and coatings. The field of nanotechnology takes advantage of nanomaterials where unique properties stem from the small size and high surface-area-to-volume ratio. In this work, we use cellulose, the most abundant natural polymer on earth, in the form of cellulose nanocrystals (CNCs). These nanoparticles are extracted from pulp, cotton, and other natural resources to yield nanometer-sized rigid rod-like particles. CNCs have recently gained attention in research and the media because of their new industrial production and “safe nanomaterial” designation in Canada. In this work, CNCs were chemically modified by the attachment of new molecules or by coating them with polymers and were subsequently added during the synthesis of the polymer latex. Incorporating CNCs imparted new properties and the ability to control latex size, shape, and surface topography. CNCs are also expected to improve the overall mechanical strength of the latex, and may enhance the stickiness of adhesive latexes in particular, leading to products that are more environmentally friendly and that show improved performance.

Iron is among the essential micronutrients for all living organisms and is a cofactor for many cellular redox reactions. Although iron is a highly abundant metal element found in the earth’s crust, it is also a limiting factor in plant development when it is present as insoluble ferric oxides. Plants have evolved two strategies to acquire soluble iron referred to as Strategy I and Strategy II. Our lab has focused on the Arabidopsis thaliana double mutant ysl1ysl3. The mutants display a chlorotic phenotype and are unable to correctly respond to iron deficiency. Grafting is a common method for joining different plant tissues and has been used for studies of long distance signaling. Past studies of iron signaling in Arabidopsis have not been able to provide a mechanism for how plants are able to signal the iron status of the shoot, where iron demand is high, to roots, where iron uptake occurs. The iron signaling experiments included in this thesis follow a seedling-graft approach to understand if grafts are capable of properly sensing iron. A longstanding question of iron homeostasis in plants is the identity of the iron sensors in plants. It was hypothesized that YSL1 and YSL3 have both a transporter function and a receptor function, and therefore function as transceptors. In our predicted model it was proposed that YSL1 and/or YSL3 are directly involved in iron status signaling either in perception and/or transmission of the signal. As evidenced through seedling grafting experiments here, YSLs play a critical part of long distance signaling that plant shoots use to signal their iron status to the roots. In this thesis, YSL1 and YSL3 are shown to be required in the shoots in order for signaling to occur correctly in the roots. To facilitate the analysis of gene expression in the grafts, a FRO3promoter:GUS construct was used in the Col-O WT background. The FRO3 promoter was selected because it is expressed in both leaves and roots under iron deficiency. Experiments showed that the genotype of the shoot used in the grafts is critical for Fe-deficiency induced gene expression in the roots. Thus, grafting has revealed that root iron deficiency responses require YSL1 and YSL3 in leaves for signal transmission. This directly links them to long-distance signaling, and supports the idea that these proteins could be acting as transceptors.

Among several early-season insect pests threatening apple production in eastern North America, plum curculio (PC), Conotrachelus nenuphar Herbst (Coleoptera: Curculionidae), is one of the most devastating pests of pome and stone fruits. Historically, several methods have been used to monitor and control plum curculio in apple orchards. The odor-baited trap tree approach has proven to serve as an effective monitoring and attract-and-kill system for plum curculio. The synergistic lure consisting of benzaldehyde (a plant volatile) and grandisoic acid (the PC aggregation pheromone) is used in this approach. However, the high cost of the lure and the degradation of benzaldehyde by UV light and heat have resulted in limited grower adoption. The major goals of this study were (1) to evaluate under field conditions, the attractiveness of methyl salicylate (MES) to PC, and to determine if it can replace the benzaldehyde (BEN), and (2) to test whether we can manipulate insect pest behavior through host plant preference by grafting selected perimeter- row trees with multiple cultivars. My results indicated that (1) methyl salicylate in combination with grandisoic acid was as attractive to PC as the standard synergistic lure composed of benzaldehyde and grandisoic acid, therefore MES can be used as a replacement for BEN, (2) trees grafted with six cultivars were more attractive to PC and concentrated more PC fruit injuries, compared to non-grafted trees, and (3) ‘Wickson’ and ‘Red Astrachan’ received numerically more PC injuries while ‘Dabinett’ received the lowest level of injury compared with other cultivars. These results highlight that a semiochemical-based strategy is a low-cost and grower-friendly approach to monitoring and controlling the PC population.

In 2007 and 2008 more than 100 million dollars of fresh market tomatoes were grown in Virginia, with the majority of production occurring on the Eastern Shore of Virginia (ESV), according to the National Agricultural Statistics Service. Bacterial wilt of tomato, caused by Ralstonia solanacearum (Smith) and Yabucchi et al., is the most devastating disease of tomato on the ESV. Four 'observational trials' were conducted on the ESV over three growing seasons to determine the temporal and spatial distribution of this disease in commercial tomato fields. Plants were assessed at approximately one-week intervals throughout the growing seasons and the incidence of bacterial wilt for each individual plant was recorded. A steady increase in both disease incidence and clustered distribution of the disease within rows was observed as the growing season progressed. Positive correlations between disease incidence and percentage of rows exhibiting a significant clustered distribution occurred in all trials, which indicated an increase in clustered distribution as disease incidence increased. Research trials were conducted over three years, beginning in the summer of 2007, to investigate the effects of tomato bacterial wilt resistant cultivars on the ESV. In 2008 and 2009, the selective, systemic compound which induces host plant resistance, acibenzolar-S-methyl (ASM) was incorporated into resistant cultivar trials. Results from the 2007 trial revealed significant resistance in some of the breeding lines, CRA 66 and PI 126408. The 2008 and 2009 trials revealed that ASM was not effective at reducing levels of bacterial wilt. Grafted transplants in the spring trials of 2008 and 2009 had varied results in resistance and yield. Results revealed the tomato cultivar BHN 669 was an excellent resistant cultivar with promising yield potential and fruit quality. / Master of Science

Eggplant grafting implemented implemented in two field sites in the Philippines, in Nueva Ecija and Pangasinan are used as proofs of concept to illustrate and validate the feasibility of an impact assessment framework for determining the nutritional impact of technology-oriented agricultural activities. Nutritional impacts are assessed by disaggregating the market demand curve into demand curves by income groups using their separate price elasticities of demand. Considering only price effects, the increase in yields following a per unit cost reduction due to eggplant grafting has positive effects on the daily caloric intake per capita in the different income classes with the greatest impact on the lowest income class for both sites. Net increases in calorie intake ranges between 0.09 and 0.6 kilocalories per capita per day. / Master of Science