Bond strength is classically characterized into two separate factors; area of the bond and specific bond strength. This separation is especially important in pulps that lack strength properties, and are specifically used for their optical properties, such as mechanical pulps. In this research the applicability of the Ingmansson and Thode method for distinguishing between specific bonded area and specific bond strength in mechanical pulps is studied. It is shown that the rigid, non-collapsable, nature of the mechanical pulp can be overcome by press drying the sheets until they approach their 50% relative humidity moisture content. Mechanical pulps have been assumed to operate in a domain where fiber failure can be considered insignificant, and the bonded area to tensile strength relationship is linear. In this study it was shown that most commercial pulps operate in a significant fiber failure domain. However, it is shown that pure fines and fines rich mechanical pulp better follow a linear bonded area to tensile strength relationship rather than a non-linear (significant fiber failure) model, suggesting that only the fiber fraction undergoes fiber failure and the finer fractions predominantly bond failure. The Ingmansson and Thode method relies on the use of scattering coefficient as a measure of specific surface area. It is shown that scattering coefficient is an accurate estimate of mechanical pulp specific surface area at a constant wavelength of light, provided that the wavelength used to measure scattering coefficient is above the significant absorption limit.

Nanoscale colloidal particles display fascinating electronic, optical and reinforcement properties as a consequence of their dimensions. Stable dispersions of nanoscale colloids find applications in drug delivery, biodiagnostics, photonic and electronic devices, and polymer nanocomposites. Most nanoparticles are unstable in dispersions and polymeric surfactants are added generally to improve dispersability and control self-assembly. However, the effect of polymeric modifiers on nanocolloid properties is poorly understood and design of modifiers is guided usually by empirical approaches. Monte Carlo simulations are used to gain a fundamental molecular-level understanding of the effect of modifiers properties on the thermodynamics and interaction forces of nanoscale colloidal particles. A novel method based on the expanded ensemble Monte Carlo technique has been developed for calculation of the chemical potential of colloidal particles in colloid-polymer mixtures (CPM). Using this method, the effect of molecular parameters like colloid diameter, polymer chain length, colloid-polymer interaction strength, and colloid and polymer concentrations, on the colloid chemical potential is investigated for both hard-sphere and attractive Lennard-Jones CPM. The presence of short-chain polymeric modifiers reduces the colloid chemical potential in attractive as well as athermal systems. In attractive CPM, there is a strong correlation between polymer adsorption and colloid chemical potential, as both show a similar dependence on the polymer molecular weight. Based on the simulation results, simple scaling relationships are proposed that capture the functional dependence of the thermodynamic properties on the molecular parameters. The polymer-induced interaction forces between the nanoparticles have been calculated as a function of the above parameters for freely-adsorbing and end-grafted homopolymer modifiers. The polymer-induced force profiles are used to identify design criteria for effective modifiers. Adsorbing modifiers give rise to attractive interactions between the nanoparticles over the whole parameter range explored in this study. Grafted surface modifiers lead to attraction or repulsion based on the polymer chain length and grafting density. The polymer-induced attraction in both adsorbing and grafted modifiers is attributed primarily to polymer intersegmental interactions and bridging. The location of the thermodynamic minimum corresponding to the equilibrium particle spacing in nanoparticle-polymer mixtures can be controlled by tuning the modifier properties.

In this research, the amorphous/nanocrystalline ZrCu/Cu multilayered thin films with various conditions such as individual layer thickness, total layer thickness, and interface type have been successfully fabricated by the multi-gun sputtering processes. To investigate the mechanical properties and deformation behaviors of substrate-supported ZrCu/Cu multilayered thin films, these films deposited on the Cu or polyimide foils were prepared for tensile testing. Firstly, the tensile behaviors of the monolithic ZrCu thin film metallic glass and the ZrCu/Cu multilayered thin films deposited on the pure Cu foils are systematically examined. The extracted tensile modulus and strength of the 1-£gm-thick multilayered thin films are in good agreement with the theoretical iso-strain rule of mixture prediction. The extracted 2-£gm-thick multilayered film data are lower, but can be corrected back by considering the actual intact cross-sectional area during the tensile loading. Moreover, the current results reveal that the ZrCu/Cu multilayered coating exhibit much better tensile performance than the monolithic ZrCu coating. It indicates that the amorphous/nanocrystalline multilayered thin film structure can certainly enhance the mechanical properties of monolithic thin film metallic glasses under tension. Secondly, for the further investigation of tensile response, the polyimide-supported amorphous/nanocrystalline ZrCu/Cu multilayered thin films with various individual layer thicknesses from 10 to 100 nm were prepared. The relatively soft, smooth, and flexible polyimide foils as the substrates in this experiment can undergo sufficient deformation under In this research, the amorphous/nanocrystalline ZrCu/Cu multilayered thin films with various conditions such as individual layer thickness, total layer thickness, and interface type have been successfully fabricated by the multi-gun sputtering processes. To investigate the mechanical properties and deformation behaviors of substrate-supported ZrCu/Cu multilayered thin films, these films deposited on the Cu or polyimide foils were prepared for tensile testing. Firstly, the tensile behaviors of the monolithic ZrCu thin film metallic glass and the ZrCu/Cu multilayered thin films deposited on the pure Cu foils are systematically examined. The extracted tensile modulus and strength of the 1-£gm-thick multilayered thin films are in good agreement with the theoretical iso-strain rule of mixture prediction. The extracted 2-£gm-thick multilayered film data are lower, but can be corrected back by considering the actual intact cross-sectional area during the tensile loading. Moreover, the current results reveal that the ZrCu/Cu multilayered coating exhibit much better tensile performance than the monolithic ZrCu coating. It indicates that the amorphous/nanocrystalline multilayered thin film structure can certainly enhance the mechanical properties of monolithic thin film metallic glasses under tension. Secondly, for the further investigation of tensile response, the polyimide-supported amorphous/nanocrystalline ZrCu/Cu multilayered thin films with various individual layer thicknesses from 10 to 100 nm were prepared. The relatively soft, smooth, and flexible polyimide foils as the substrates in this experiment can undergo sufficient deformation under tension. The modulus and strength of the multilayered thin film are again demonstrated to be consistent with the theoretical iso-strain rule of mixture values. As the individual layer thickness decreases from 100 to 10 nm, the Young¡¦s moduli are only varied slightly. However, the maximum tensile stress exhibits a highest value for the 25 nm layer thickness. The higher crack spacing, or the lower crack density, of this 25 nm multilayer film leads to the highest strength. Thirdly, to avoid the stress and strain incompatibility owing to the mismatch of elastic modulus and strength levels from the connected amorphous/nanocrystalline layers, the Cu-supported amorphous/nanocrystalline ZrCu/Cu multilayered thin films with sharp and graded interfaces were successfully sputtered and examined by tensile testing. The extracted tensile properties of the multilayered films can be compared with the predicted values based on the two-phase and three-phase iso-strain rule of mixture model. The multilayered films with graded interfaces, each about 50 nm thick, consistently exhibit higher tensile strength and elongation. This can be rationalized by the reduced stress and strain incompatibility along the interfaces.

Fatigue cracking and moisture damage are two important modes of distresses in asphalt pavements. Recently, the Dynamic Mechanical Analyzer (DMA) was used to characterize fatigue cracking and evaluate the effects of moisture damage on the Fine Aggregate Matrix (FAM) portion of asphalt mixtures. The FAM specimens should be properly fabricated to represent the composition and structure of the fine portion of the mixture. The objective of the first phase of this study was to develop a standard test procedure for preparing FAM specimens such that it is representative of the mixture. The method consists of preparing loose full asphalt mixtures and sieving through different sizes. Then, the ignition oven was used to determine the binder content associated with the small size materials (passing on sieve #16). Sieve #16 is used to separate fine aggregates from the coarse aggregates. The applicability of this new method will be evaluated using a number of asphalt mixtures. The objective of the second phase of this study was to develop software to analyze the data from DMA test. Such software will enable engineers and researchers to perform the complex analysis in very short time. This is Microsoft Windows ® based software, executable in any hardware configuration under this operational system.

This dissertation focuses on developing a predictive method for determining the dynamic densification behavior of thermite powder mixtures consisting of equivolumetric mixtures of Ta + Fe₂O₃ and Ta + Bi₂O₃. Of primary importance to these highly reactive powder mixtures is the ability to characterize the stress at which full compaction occurs, the crush strength, which can significantly influence the stress required to initiate reaction during dynamic or impact loading. Examined specifically are the quasi-static and dynamic compaction responses of these mixtures. Experimentally obtained compaction responses in the quasi-static regime are analyzed using available compaction models, and an analysis technique is developed that allows for a correct measurement of the apparent yield strength of the powder mixtures. The correctly determined apparent yield strength is combined with an equation of state to yield a prediction of the shock densification response, including the dynamic crush strength of the thermite powder mixtures. The validated approach is also extended to the Al + Fe₂O₃ thermite system. It is found that accurate predictions of the crush strength can be obtained through determination of the apparent yield strength of the powder mixture when incorporated into the equation of state. It is observed that the predictive ability in the incomplete compaction region is configurationally dependent for highly heterogeneous thermite powder systems, which is in turn influenced by particle morphology and differences in intrinsic properties of constituents (density, strength, etc.).

Studies show that the microstructure of the fine aggregate matrix has a significant influence on the mechanical properties and evolution of damage in an asphalt mixture. However, very little work has been done to quantitatively characterize the microstructure of the asphalt binder within the fine aggregate matrix of asphalt mixtures. The first objective of this study was to quantitatively characterize the three dimensional microstructure of the asphalt binder within the fine aggregate matrix (FAM) of an asphalt mixture and compare the influence of binder content, coarse aggregate gradation, and fine aggregate gradation on this microstructure. Studies indicate that gradation of the fine aggregate has the most influence of the degree of anisotropy whereas gradation of the coarse aggregate has the most influence on the direction anisotropy of the asphalt mastic within the fine aggregate matrix. Addition of asphalt binder or adjustments to the fine aggregate gradation also resulted in a more uniform distribution of the asphalt mastic within the fine aggregate matrix. The second objective of this study was to compare the internal microstructure of the mortar within a full-scale asphalt mixture to the internal microstructure of the FAM specimen and also conduct a limited evaluation of the influence of mixture properties and methods of compaction on the engineering properties of the FAM specimens. Fatigue cracking is a significant form of pavement distress in flexible pavements. The properties of the sand-asphalt mortars or FAM can be used to characterize the evolution of fatigue crack growth and self-healing in full-scale asphalt mixtures. The results from this study, although limited in number, indicate that in most cases the SGC (Superpave Gyratory Compactor) compacted FAM specimen had a microstructure that most closely resembled the microstructure of the mortar within a full-scale asphalt mixture. Another finding from this study was that, at a given level of damage, the healing characteristic of the three different types of FAM mixes evaluated was not significantly different. This indicates that the healing rate is mostly dictated by the type of binder and not significantly influenced by the gradation or binder content, as long as the volumetric distribution of the mastic was the same. / text

Separation of aromatic/aliphatic hydrocarbon mixtures by pervaporation has been of increasing interest in recent decades. Dozens of polymer materials have been reported for separations of benzene/cyclohexane and toluene/iso-ocatne mixtures. However, fundamental understanding of material structure and transport relations is not adequate to generalize guidelines for materials screening. The goals of this study are to tailor the structure of the polyimide materials, correlate the structure and transport relations, and establish guidelines for future materials. The 3, 5-Diaminobenzoic acid (DABA) containing polyimides were synthesized by both chemical and thermal solution imidization. The synthesized polyimides were formed into dense films by solution casting. The physical properties of the polyimides synthesized with monomers: 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4, 6-trimethyl-1, 3-phenylendiamine (DAM) and DABA, were characterized by DSC, WAXD, GPC and density. The chemical structures were assessed by FTIR and NMR. The pervaporation and sorption of the synthesized polyimide membranes were tested in toluene/iso-octane mixtures at 100°C. The structure- transport property relations were established for the 6FDA-DAM/DABA membranes. The 6FDA-DAM/DABA polyimides were crosslinked by ethylene glycol. The pervaporation and sorption of the crosslinked membranes were tested in toluene/iso-octane mixtures at 100°C. Thermal imidization was found to give a higher imidization degree than chemical imidization. As a result, the polyimides made by chemical imidization contain a higher percentage of carboxylic acid groups than those made by thermal imidization. Chemical imidization gives higher film density, glass transition temperature and lower flux and higher selectivity for the toluene/iso-octane pervaporation than the thermally imidized membranes because of the higher carboxylic acid concentration. The chemically imidized membranes are slightly brittle after the crosslinking. Only the thermal imidization membranes have good flexibility and its pervaporation selectivity improves significantly after the crosslinking. Solubility selectivity and diffusivity selectivity of the 6FDA-DAM/DABA membranes were correlated with solubility parameters and fractional free volume, respectively. The structure-mass transport relations show that for the 6FDA-DAM/DABA membranes, both solubility selectivity and diffusivity selectivity contribute to the pervaporation selectivity. For the chemically imidized membranes, increased DABA concentration has a positive effect on solubility selectivity and diffusivity selectivity. For the thermally imidized membranes, increased DABA concentration has a significant effect on diffusivity selectivity only. / text

Platinum complexes (cisplatin, carboplatin and oxaliplatin) are effective anticancer agents. However the major drawbacks of platinum chemotherapy are toxic side effects and resistance. The affinity of platinum complexes to sulfur donor ligands of side chains of methionine and cysteine amino acids was assumed to be responsible for toxicity and resistance. Recently, it was found that the reaction of platinum complex with proteins containing sulfur donor ligands could actually favor its anticancer activity. Copper transporter 1 (Ctr 1), a protein involved in the transport of copper into the cell, also helps in the influx of cisplatin by binding to N-terminal domain of Ctr 1 which is rich in methionine and histidine residues. A better understanding of how the size and shape of amine ligand, and leaving groups affect the reaction of platinum (II) complexes with methionine could give new ways to optimize its anticancer activity. This preliminary research focuses to answer this by HPLC-UV-VIS analysis of bulky platinum complexes including [Pt(dien)Cl]Cl, Pt(Me4en)(NO3)2 and Pt(en)(NO3)2 with two methionine containing small peptides that serve as models for protein interactions.

This thesis was concerned with the proof of concept for mid-grade, 250-500oC, industrial waste heat recovery using a thermally regenerative electrochemical system. Proposed thermally regenerative electrochemical systems are limited to high operating temperatures (> 900oC) and suffer from poor conversion efficiencies (< 20%). As such, a single chamber design that is free of moving parts was presented in this work. The concept for this novel regenerative system relies on gravity and a liquid medium to convey dissolved sodium hydride in a hydride-borohydride solution from cold to hot regions in a continuous circuit. Such a liquid transport medium could allow for operation below 500oC while stabilizing the hydride from thermal decomposition. Investigations on this system were carried out using a custom pressure differential thermal analyzer that was able to operate above temperatures of 700oC and pressures of 2.2MPa. The results of the experiments provided valuable information concerning the phase diagrams of various hydride-borohydride mixtures. The eutectic composition of the NaH-KBH4 system was found to be 43 mole% NaH. The corresponding eutectic temperature (503oC) was determined using the differential cooling curves. Appreciable NaH decomposition was noticed in mixtures above 59.0 mole% NaH. Mixtures up to 42.5 mole% KH in KBH4 were also investigated. The eutectic composition of the KH-KBH4 binary system was determined by extrapolating the liquidus curve to intersect the solidus curve. The KH-KBH4 eutectic temperature was found to be 390oC at 66 mole% KH. The experimental work successfully demonstrates that thermally unstable hydrides can be obtained in the liquid phase below their melting points, under moderate pressures, when mixed with alkali borohydrides. This significantly lowers the achievable operating temperature of the thermally regenerative electrochemical systems currently proposed. The use of the single chamber design with a hydride-borohydride liquid medium offers numerous advantages including: reduced maintenance, reduced operating temperature, reduced system weight, reduced parasitic losses, increased voltage, and increased reliability. The viability for mid-grade industrial waste heat recovery requires construction of a prototype which optimizes power outputs and explores the hydrodynamic transport of material. / Thesis (Master, Mining Engineering) -- Queen's University, 2009-09-24 14:33:22.627

Natural geomaterials exhibit a wide range in size, physical properties, chemical properties, and mechanical behaviors. Soils that are composed of mixtures of particles with different physical and chemical properties pose a challenge to characterization and quantification of the engineering properties. This study examined the behavior of particulate mixtures composed of differently sized silica particles, mixtures composed of aluminosilicate and organic carbon particles, and mixtures composed of particles with approximately three orders of magnitude difference in particle size. This experimental investigation used elastic, electromagnetic, and thermal waves to characterize and to quantify the small to intermediate strain behavior of the mixtures. The mechanical property of stiffness of mixed materials (e.g. binary mixtures of silica particles and fly ashes with various carbon and biomass contents) was evaluated through the stiffness of active grain contacts, and the stiffness of particles which carry applied load, using the physical concepts of intergranular void ratio and interfine void ratio. Additionally, the change in both contact mode/stiffness and electrical property due to the presence of nano-sized particles (i.e., iron oxides) on the surface of soil grains was evaluated according to applied stress, packing density, iron coating density, and substrate sand particle size. Finally, the biomass fraction and total organic carbon content of mixtures was used to quantify the electrical and thermal conductivities when particulate organic was mixed with aluminosilicate particles.