A numerical tool has been developed for particle-level simulations of fibre suspension flows, particularly forming of the fibre network structure of paper sheets in the paper machine. The model considers inert fibres of various equilibrium shapes, and finite stiffness, interacting with each other through normal, frictional, and lubrication forces, and with the surrounding fluid medium through hydrodynamic forces. Fibre–fluid interactions in the non-creeping flow regime are taken into account, and the two-way coupling between the solids and the fluid phases is included by enforcing momentum conservation between phases. The incompressible three-dimensional Navier–Stokes equations are employed tomodel themotion of the fluid medium. The validity of the model has been tested by comparing simulation results with experimental data from the literature. It was demonstrated that the model predicts well the motion of isolated fibres in shear flow over a wide range of fibre flexibilities. It was also shown that the model predicts details of the orientation distribution of   multiple, straight, rigid fibres in a sheared suspension. Furthermore, model predictions of the shear viscosity and first normal stress difference were in fair agreement with experimental data found in the literature. Since the model is based solely on first principles physics, quantitative predictions could be made without any parameter fitting.   Based on these validations, a series of simulations have been performed to investigate the basic mechanisms responsible for the development of the stress tensor components for monodispersed, non-Brownian fibres suspended in a Newtonian fluid in shear flow. The effects of fibre aspect ratio, concentration, and inter-particle friction, as well as the tendency of fibre agglomeration, were examined in the nonconcentrated regimes. For the case of well dispersed suspensions, semi-empirical relationships were found between the aforementioned fibre suspension properties, and the steady state apparent shear viscosity, and the first/second normal stress differences.   Finally, simulations have been conducted for the development of paper structures in the forming section of the paper machine. The conditions used for the simulations were retrieved from pilot-scale forming trial data in the literature, and from real pulp fibre analyses. Dewatering was simulated by moving two forming fabrics toward each other through a fibre suspension. Effects of the jet-to-wire speed difference on the fibre orientation anisotropy, the mass density distribution, and three-dimensionality of the fibre network, were investigated. Simulation results showed that the model captures well the essential features of the forming effects on these paper structure parameters, and also posed newquestions on the conventional wisdom of the forming mechanics.

The thermal histories of terrestrial planets are investigated using two parameterized mantle convection models for either Earth like planets and planets with no active plate tectonics. Using parameterized models of mantle convection, we performed computer simulations of planetary cooling and volatile cycling. The models estimate the amount of volatile in mantle reservoir, and calculate the outgassing and regassing rates. A linear model of volatile concentration-dependent is assumed for the activation energy of the solid-state creep in the mantle. The kinematic viscosity of the mantle is thus dynamically affected by the activation energy through a variable concentration in volatile. Mantle temperature and heat flux is calculated using a model derived from classic thermal boundary layer theory of a single layered mantle with temperature dependent viscosity. The rate of volatile exchanged between mantle and surface is calculated by balancing the amount of volatiles degassed in the atmosphere by volcanic and spreading related processes and the amount of volatiles recycled back in the mantle by the subduction process. In the cases that lack plate tectonics, the degassing efficiency is dramatically reduced and the regassing process is absent. The degassing effect is dependent on average spreading rate of tectonic plates and on the amount of volatile in the melt extract in the transition zone between mantle and upper boundary laver. The regassing effect is dependent on the subduction rate and on the amount of volatile present on a hydrated layer on top of the subducting slab. The degassing and regassing parameters are all related to the intensity of the convection in the mantle and to the surface temperature of the planet, and they are regulated by the amount of volatiles in reservoir. Comparative study with the previous models display significant differences and improve the versatility of the model. The optimum efficiency factors found are in the range of 0.01-0.06 for degassing/regassing processes, in agreement with more recent estimates. An important effect of the volatile cycling process is a general negative feedback effect that results in a general trend to adjust the mantle volatile content in time to a value set by the energy balance in the system. As a result, the initial amount of volatile in the mantle is rendered irrelevant for late stage of thermal evolution. In the case of no plate tectonics, the opposite effect takes place: initial volatilization plays an important role through entire evolution. The implications of mantle convection on the stability of the lithosphere were investigated further using the thermal history calculations and numeric simulations. They point to the conclusion that mantle convection induced stress levels increase from the past to the present fact that leads to a greater potential of craton deformation. The main consequence of this trend is that sections of continental lithosphere that have remained stable since the Archean and Proterozoic are becoming progressively more prone to instability in the geologically modem era. After the volatiles are degassed from the mantle, they are cycled through the atmosphere. The interact with the climate influencing the surface temperature, and further controlling the mantle convection. Using a grey radiative-convective model for the atmosphere, we analyzed the feedback relationships between volatiles, especially water, and surface temperature. We showed that large amount of water degassed during a hot, possible melt ocean phase after the planet formation could conserve large amount of water in atmosphere and maintain the surface temperature at moderate level.

This thesis aims to improve the performance of latex-based pressure-sensitive adhesives (PSAs). PSA performance is usually evaluated by tack, peel strength and shear strength. Tack and peel strength characterize a PSA’s bonding strength to a substrate while shear strength reflects a PSA’s capability to resist shear deformation. In general, increasing shear strength leads to a decrease in tack and peel strength. While there are several commercial PSA synthesis methods, the two most important methods consist of either solvent-based or latex-based techniques. While latex-based PSAs are more environmentally compliant than solvent-based PSAs, they tend to have much lower shear strength, at similar tack and peel strength levels. Therefore, the goal in this thesis was to greatly improve the shear strength of latex-based PSAs at little to no sacrifice to tack and peel strength. In this study, controlling the polymer microstructure of latexes or their corresponding PSA films was used as the main method for improving the PSA performance. The research was sub-divided into four parts. First, the influence of chain transfer agent (CTA) and cross-linker on latex polymer microstructure was studied via seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA). Three techniques were used to produce the latexes: (1) adding CTA only, (2) adding cross-linker only, and (3) adding both CTA and cross-linker. It was found that using CTA and cross-linker simultaneously allows one to expand the range of latex microstructural possibilities. For example, latexes with similar gel contents but different Mc (molecular weight between cross-links) and Mw (molecular weight of sol polymers) could be produced if CTA and cross-linker concentration are both increased. However, for the corresponding PSAs with similar gel contents, the relationship between their polymer microstructure and performance was difficult to establish as almost all of the medium and high gel content PSAs showed very low tack and peel strength as well as extremely large shear strength readings. In the second part of this thesis, in order to improve the tack and peel strength of medium and high gel content PSAs, the monomer composition and emulsifier concentration were varied. It was found that changing the monomer mixture from BA/MMA to BA/acrylic acid (AA)/2-hydroxyethyl methacrylate (HEMA) while simultaneously decreasing emulsifier concentration dramatically improved the corresponding PSAs’ shear strength as well as tack and peel strength. The addition of polar groups to the PSA increased its cohesive strength due to the presence of strong hydrogen bonding; meanwhile, PSA films’ surface tension increased. In the third part, two series of BA/AA/HEMA latexes were generated by varying the amounts of CTA either in the absence or presence of cross-linker. The latexes produced in the absence of cross-linker exhibited significantly larger Mc and Mw compared to their counterparts with similar gel contents prepared with cross-linker. The PSAs with the larger Mc and Mw showed much larger shear strengths due to improved entanglements between the polymer chains. In the final part of the thesis, the performance of the BA/AA/HEMA PSAs was further improved by post-heating. Compared with original latex-based PSAs with similar gel contents, heat-treated PSAs showed not only significantly improved shear strengths, but also much larger tack and peel strengths. The different shear strengths were related to the PSAs’ gel structures, which were discrete in the original PSAs but continuous in the heat-treated PSAs. The improved tack and peel strengths were related to the PSA films’ surface smoothness. During the post-heating process, the PSA polymer flowed, resulting in much smoother surfaces than the original PSA films. In addition, the effect of post-heating was related to the polymer microstructure of the untreated PSAs. Decreasing the amount of very small or very big polymers or simultaneously increasing Mc and Mw could lead to post-treated PSAs with significantly better performance. Moreover, it was found that by optimizing the polymer microstructure of the original latex-based PSAs, it was possible to obtain a treated PSA with similar or even better performance than a solvent-based PSA with similar polymer microstructure. Our original objective was surpassed: in two cases, not only was shear strength greatly improved, but so were tack and peel strength due to the simultaneous modification of PSA bulk and surface properties.

The main objective of this study was to investigate micro and nano cacao fibers and their effects on quality, texture and staling of cakes. In the first part of the study, rheological properties of cake batter with different concentrations (0 %, 3 %, 6 %, 9 %, 12 %) cacao micro and nano fiber, and cacao powder were determined. Cake batter was found to show shear thinning and time independent behavior for all formulations and fit the Power Law model. The viscosity increased as the percentage of fiber increased. Both G&rsquo / and G&rsquo / &rsquo / values increased with oscillatory frequency and percentage of fiber. In the second part of the study, physical properties (specific volume, texture, color and weight loss), sensory properties of cakes and textural changes during storage were determined. Addition of micro and nano cacao fibers to the cake formulation decreased specific volume, weight loss and L* values. It increased hardness, springiness, chewiness, resilience and elastic recovery values and minimized textural changes during storage. Fiber addition also improved the cake acceptability of the cakes in terms of odor, taste and color.

This thesis aims to improve the performance of latex-based pressure-sensitive adhesives (PSAs). PSA performance is usually evaluated by tack, peel strength and shear strength. Tack and peel strength characterize a PSA’s bonding strength to a substrate while shear strength reflects a PSA’s capability to resist shear deformation. In general, increasing shear strength leads to a decrease in tack and peel strength. While there are several commercial PSA synthesis methods, the two most important methods consist of either solvent-based or latex-based techniques. While latex-based PSAs are more environmentally compliant than solvent-based PSAs, they tend to have much lower shear strength, at similar tack and peel strength levels. Therefore, the goal in this thesis was to greatly improve the shear strength of latex-based PSAs at little to no sacrifice to tack and peel strength. In this study, controlling the polymer microstructure of latexes or their corresponding PSA films was used as the main method for improving the PSA performance. The research was sub-divided into four parts. First, the influence of chain transfer agent (CTA) and cross-linker on latex polymer microstructure was studied via seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA). Three techniques were used to produce the latexes: (1) adding CTA only, (2) adding cross-linker only, and (3) adding both CTA and cross-linker. It was found that using CTA and cross-linker simultaneously allows one to expand the range of latex microstructural possibilities. For example, latexes with similar gel contents but different Mc (molecular weight between cross-links) and Mw (molecular weight of sol polymers) could be produced if CTA and cross-linker concentration are both increased. However, for the corresponding PSAs with similar gel contents, the relationship between their polymer microstructure and performance was difficult to establish as almost all of the medium and high gel content PSAs showed very low tack and peel strength as well as extremely large shear strength readings. In the second part of this thesis, in order to improve the tack and peel strength of medium and high gel content PSAs, the monomer composition and emulsifier concentration were varied. It was found that changing the monomer mixture from BA/MMA to BA/acrylic acid (AA)/2-hydroxyethyl methacrylate (HEMA) while simultaneously decreasing emulsifier concentration dramatically improved the corresponding PSAs’ shear strength as well as tack and peel strength. The addition of polar groups to the PSA increased its cohesive strength due to the presence of strong hydrogen bonding; meanwhile, PSA films’ surface tension increased. In the third part, two series of BA/AA/HEMA latexes were generated by varying the amounts of CTA either in the absence or presence of cross-linker. The latexes produced in the absence of cross-linker exhibited significantly larger Mc and Mw compared to their counterparts with similar gel contents prepared with cross-linker. The PSAs with the larger Mc and Mw showed much larger shear strengths due to improved entanglements between the polymer chains. In the final part of the thesis, the performance of the BA/AA/HEMA PSAs was further improved by post-heating. Compared with original latex-based PSAs with similar gel contents, heat-treated PSAs showed not only significantly improved shear strengths, but also much larger tack and peel strengths. The different shear strengths were related to the PSAs’ gel structures, which were discrete in the original PSAs but continuous in the heat-treated PSAs. The improved tack and peel strengths were related to the PSA films’ surface smoothness. During the post-heating process, the PSA polymer flowed, resulting in much smoother surfaces than the original PSA films. In addition, the effect of post-heating was related to the polymer microstructure of the untreated PSAs. Decreasing the amount of very small or very big polymers or simultaneously increasing Mc and Mw could lead to post-treated PSAs with significantly better performance. Moreover, it was found that by optimizing the polymer microstructure of the original latex-based PSAs, it was possible to obtain a treated PSA with similar or even better performance than a solvent-based PSA with similar polymer microstructure. Our original objective was surpassed: in two cases, not only was shear strength greatly improved, but so were tack and peel strength due to the simultaneous modification of PSA bulk and surface properties.

Studies show that dynamical properties of ultra-thin polymer films deviate from those of bulk materials. Despite some controversial issues, there is growing evidence indicating that the interfacial properties play a key role for observed dynamical anomalies. However, how and how much the interfacial properties affect the average dynamics of the nanometer scale systems are still elusive. In this work, we developed several novel techniques to investigate near-free-surface dynamics of thin polymer films. We studied surface dynamics of glassy i-PMMA films using a nano surface hole relaxation technique: a strong substrate property dependence and an unexpected molecular weight dependence were observed; we found that a local Tg of ~40K below bulk Tg could be assigned to the surface region. We used nano gold particle embedding to study PS surface dynamics: enhanced surface dynamics and weak temperature dependence were observed for the surface region; a depth profile with the nm resolution was observed; viscous liquid-like and soft solid-like properties were observed in the first 5.5nm and next 3.3 nm regions in PS films; no molecualr weight dependence was found in glassy PS films. We built a low level noise measurement system to study the thermal polarization noise in PVAc films: cooperative rearranging dynamics were evidenced; the noise power spectral density (PSD) is found to fluctuate around a certain average level without discernable peak shift; we observed some relatively big jumps or fluctuations in successive integrated PSD’s, which indicate some energy exchange between different microscopic domains in glassy polymer systems. We developed a novel nano rheology AFM technique to study the near-free-surface dynamics of thin polymer films: enhanced near-free-surface dynamics with weak temperature dependence are observed for PVAc films, which is similar with the PS case.

Studies show that dynamical properties of ultra-thin polymer films deviate from those of bulk materials. Despite some controversial issues, there is growing evidence indicating that the interfacial properties play a key role for observed dynamical anomalies. However, how and how much the interfacial properties affect the average dynamics of the nanometer scale systems are still elusive. In this work, we developed several novel techniques to investigate near-free-surface dynamics of thin polymer films. We studied surface dynamics of glassy i-PMMA films using a nano surface hole relaxation technique: a strong substrate property dependence and an unexpected molecular weight dependence were observed; we found that a local Tg of ~40K below bulk Tg could be assigned to the surface region. We used nano gold particle embedding to study PS surface dynamics: enhanced surface dynamics and weak temperature dependence were observed for the surface region; a depth profile with the nm resolution was observed; viscous liquid-like and soft solid-like properties were observed in the first 5.5nm and next 3.3 nm regions in PS films; no molecualr weight dependence was found in glassy PS films. We built a low level noise measurement system to study the thermal polarization noise in PVAc films: cooperative rearranging dynamics were evidenced; the noise power spectral density (PSD) is found to fluctuate around a certain average level without discernable peak shift; we observed some relatively big jumps or fluctuations in successive integrated PSD’s, which indicate some energy exchange between different microscopic domains in glassy polymer systems. We developed a novel nano rheology AFM technique to study the near-free-surface dynamics of thin polymer films: enhanced near-free-surface dynamics with weak temperature dependence are observed for PVAc films, which is similar with the PS case.

No description available.

A new microrheology set-up is described, which allows us to quantitatively measure the transient rheological properties and microstructure of a variety of solvent-responsive complex fluids. The device was constructed by integrating particle tracking microrheology and microfluidics and offers unique experimental capabilities for performing solvent-response measurements on soft fragile materials without applying external shear forces. Transient analysis methods to quantitatively obtain rheological properties were also constructed, and guidelines for the trade-off between statistical validity and temporal resolution were developed to accurately capture physical transitions. With the new device and methodology, we successfully quantified the transient rheological and microstructural responses during gel formation and break-up, and viscosity changes of solvent-responsive complex fluids. The analysis method was expanded for heterogeneous samples, incorporating methods to quantify the microrheology of samples with broad distributions of individual particle dynamics. Transient microrheology measurements of fragile, heterogeneous, self-assembled block copolypeptide hydrogels revealed that solvent exchange via convective mixing and dialysis can lead to significantly different gel properties and that commonly applied sample preparation protocols for the characterization of soft biomaterials could lead to erroneous conclusions about microstructural dynamics. Systematic investigations by varying key parameters, like molecular structure, gel concentration, salt concentration, and tracer particle size for microrheology, revealed that subtle variations in molecular architecture can cause major structural and microrheological changes in response dynamics. Moreover, the results showed that the method can be applied for studying gel formation and breakup kinetics. The research in this thesis facilitates the design of solvent-responsive soft materials with appropriate microstructural dynamics for in vivo applications like tissue engineering and drug delivery, and can also be applied to study the effect of solvents on self-assembly mechanisms in other responsive soft materials, such as polymer solutions and colloidal dispersions.

The aim of this study was to identify QTLs associated with the maintenance of grain quality following post-anthesis heat stress. A population of 64 F6Halberd X Cutter recombinant inbred lines (RILs) was exposed to either heat stress or control conditions in the greenhouse, starting ten days after anthesis. Grain quality was determined using the sodium dodecyl sulfate (SDS) sedimentation test, a significant predictor of bread baking quality. The percent change in SDS sedimentation test scores between the heat and control populations was used to identify QTLs associated with quality stability. Four QTLs were identified, located one each on chromosomes 1B, 1D, 4A, and 7A. Three of the QTLs, those on 1B, 1D, and 4A, were associated with variations in SDS sedimentation level. The QTL on chromosome 7A was associated with the percent change in SDS sedimentation scores between heat-stressed and control conditions. This indicated a relationship between the identified QTL and quality stability. To confirm the detected QTLs, eighty advanced lines grown at three Texas nurseries were genotyped and tested for relationships between QTL-associated markers, quality traits, and stability of the quality traits. Quality trait stability was estimated using the coefficient of variability (CV%) of quality traits between growing sites. Quality characters analyzed in the advanced lines included kernel hardness, mixograph peak time, kernel weight, flour yield, SDS sedimentation, and grain yield. The analysis showed support for the effect of the QTLs on chromosomes 1B, 1D, and 4A. Further analysis will be needed to confirm the QTL on 7A, in particular. The mapping of additional markers will be necessary. However, the potential importance of this QTL and the abundance of other QTLs detected in this region make it worth investigating.