DEVELOPMENT OF A MECHANISM AND PROCESS TO CONTINUOUSLY PRODUCE SPHERICAL, TORREFIED BIOMASS PELLETS

A recently developed novel biomass fuel pellet, the Q’ Pellet, offers significant improvements over conventional white pellets, with characteristics comparable to those of coal. The Q’ Pellet was initially created at bench scale using a proprietary die and punch design, in which the biomass was torrefied in-situ¬ and then compressed. To bring the benefits of the Q’ Pellet to a commercial level, it must be capable of being produced in a continuous process at a competitive cost. A prototype machine was previously constructed in a first effort to assess continuous processing of the Q’ Pellet. The prototype torrefied biomass in a separate, ex-situ reactor and transported it into a rotary compression stage. Upon evaluation, parts of the prototype were found to be unsuccessful and required a redesign of the material transport method as well as the compression mechanism. A process was developed in which material was torrefied ex-situ and extruded in a pre-compression stage. The extruded biomass overcame multiple handling issues that had been experienced with un-densified biomass, facilitating efficient material transport. Biomass was extruded directly into a novel re-designed pelletizing die, which incorporated a removable cap, ejection pin and a die spring to accommodate a repeatable continuous process. Although after several uses the die required manual intervention due to minor design and manufacturing quality limitations, the system clearly demonstrated the capability of producing the Q’ Pellet in a continuous process. Q’ Pellets produced by the pre-compression method and pelletized in the re-designed die had an average dry basis gross calorific value of 22.04 MJ/kg, pellet durability index of 99.86% and dried to 6.2% of its initial mass following 24 hours submerged in water. This compares well with literature results of 21.29 MJ/kg, 100% pellet durability index and <5% mass increase in a water submersion test. These results indicate that the methods developed herein are capable of producing Q’ Pellets in a continuous process with fuel properties competitive with coal.

Analysis of Cosmogenic Impurities in Tellurium and Development of Tellurium Loading for the SNO+ Experiment

For the SNO+ neutrinoless double beta decay search, various backgrounds, ranging from impurities present naturally to those produced cosmogenically, must be understood and reduced. Cosmogenic backgrounds are particularly difficult to reduce as they are continually regenerated while exposed to high energy cosmic rays. To reduce these cosmogenics as much as possible the tellurium used for the neutrinoless double beta decay search will be purified underground. An analysis of the purification factors achievable for insoluble cosmogenic impurities found a reduction factor of $>$20.4 at 50\% C.L.. During the purification process the tellurium will come into contact with ultra pure water and nitric acid. These liquids both carry some cosmogenic impurities with them that could be potentially transferred to the tellurium. A conservative limit is set at $<$18 events in the SNO+ region of interest (ROI) per year as a result of contaminants from these liquids. In addition to cosmogenics brought underground, muons can produce radioactive isotopes while the tellurium is stored underground. A study on the rate at which muons produce these backgrounds finds an additional 1 event per year. In order to load the tellurium into the detector, it will be combined with 1,2-butanediol to form an organometallic complex. The complex was found to have minimal effect on the SNO+ acrylic vessel for 154 years.

Development of a Composite ion-exchange membrane for PDMS-based microfluidic devices

The purpose of this research is to investigate potential methods to produce an ion-exchange membrane that can be integrated directly into a polydimethylsiloxane Lab-on-a-Chip or Micro-Total-Analysis-System. The majority of microfluidic membranes are based on creating microporous structures, because it allows flexibility in the choice of material such that it can match the material of the microfluidic chip. This cohesion between the material of the microfluidic chip and membrane is an important feature to prevent bonding difficulties which can lead to leaking and other practical problems. However, of the materials commonly used to manufacture microfluidic chips, there are none that provide the ion-exchange capability. The DuPont product Nafion{TM} is chosen as the ion-exchange membrane, a copolymer with high conductivity and selectivity to cations and suitable for many applications such as electrolysis of water and the chlor-alkali process. The use of such an ion-exchange membrane in microfluidics could have multiple advantages, but there is no reversible/irreversible bonding that occurs between PDMS and Nafion{TM}. In this project multiple methods of physical entrapment of the ion-exchange material inside a film of PDMS are attempted. Through the use of the inherent properties of PDMS, very inexpensive sugar granulate can be used to make an inexpensive membrane mould which does not interfere with the PDMS crosslinking process. After dissolving away this sacrificial mould material, Nafion{TM} is solidified in the irregular granulate holes. Nafion{TM} in this membrane is confined in the irregular shape of the PDMS openings. The outer structure of the membrane is all PDMS and can be attached easily and securely to any PDMS-based microfluidic device through reversible or irreversible PDMS/PDMS bonding. Through impedance measurement, the effectiveness of these integrated membranes are compared against plain Nafion{TM} films in simple sodium chloride solutions.

DEVELOPMENT OF A CONDENSED PHASE VELOCITY MAP IMAGING APPARATUS: DISSOCIATION PHOTODYNAMICS OF NITROGEN DIOXIDE AT 355 NM

The photochemistry of the polar regions of Earth, as well as the interstellar medium, is driven by the effect of ultraviolet radiation on ice surfaces and on the materials trapped within them. While the area of ice photochemistry is vast and much research has been completed, it has only recently been possible to study the dynamics of these processes on a microscopic level. One of the leading techniques for studying photoreaction dynamics is Velocity Map Imaging (VMI). This technique has been used extensively to study several types of reaction dynamics processes. Although the majority of these studies have utilized molecular beams as the main medium for reactants, new studies showed the versatility of the technique when applied to molecular dynamics of molecules adsorbed on metal surfaces. Herein the development of a velocity map imaging apparatus capable of studying the photochemistry of condensed phase materials is described. The apparatus is used to study of the photo-reactivity of NO2 condensed within argon matrices to illustrate its capabilities. A doped ice surface is formed by condensing Ar and NO2 gas onto a sapphire rod which is cooled using a helium compressor to 20 K. The matrix is irradiated using an Nd:YAG laser at 355 nm, and the resulting NO fragment is state-selectively ionized using an excimer-pumped dye laser. In all, we are able to detect transient photochemically generated species and can collect information on their quantum state and kinetic energy distribution. It is found that the REMPI spectra changes as different sections of the dissociating cloud are probed. The rotational and translational energy populations are found to be bimodal with a low temperature component roughly at the temperature of the matrix, and a second component with much higher temperature, the rotational temperature showing a possible population inversion, and the translational temperature of 100-200 K. The low temperature translational component is found to dominate at long delay times between dissociation and ionization, while at short time delays the high temperature component plays a larger role. The velocity map imaging technique allows for the detection of both the axial and radial components of the translational energy. The distribution of excess energy over the rotational, electronic and translational states of the NO photofragments provides evidence for collisional quenching of the fragments in the Ar-matrix prior to their desorption.

DEVELOPMENT OF AN ADJUSTABLE SUTURE TECHNIQUE FOR TRABECULECTOMY

This research presents a new design of an adjustable suture that could provide a better intraocular pressure (IOP) control in the post treatment of trabeculectomy surgery and limit associated complication with the current suturing techniques. A better control in tension suture brings a great deal of advantages to this surgical technique compared with the traditional adjustable suture. A length adjustment can be added in advance to a 10-0 nylon suture which enables suture tension to be released during the postoperative period of trabeculectomy surgery. This adjustment has a D-ring geometry made of 10-0 nylon suture adhered to a 10-0 nylon surgical suture which is used to close the scalar flap. The D ring was adhered with about 180 microdroplet of Loctite 4311that was found to form a strong joint to connect the D ring to the main 10-0 nylon suture and strong enough to carry the added tension instead after cutting the central suture between the two joints of the D ring. The geometry of adjustment is the key factor of maintaining the IOP at the normal range and keeping the scleral flap tight enough and secure so that aqueous humor continues to percolate under the subconjunctiva. It has been found that a 365, and 450 µm length extensions can release suture tension postoperatively and relieve the intraocular pressure within the eye by 33, and 66% respectively. The fabrication process of the new adjustable suture was divided into two steps: fabrication of micro jig and forming microdroplets. A micro jig was fabricated in order to form and bond a precise length extension to the new design of the adjustable suture. In addition, a new liquid separation technique has been followed in this study in order to generate micro adhesive droplets as small as 50µm for bonding the new adjustable suture structure.

Development of An Enhanced Oil Sands Fluid Tailings Generation Model

Bitumen extraction from surface-mined oil sands results in the production of large volumes of Fluid Fine Tailings (FFT). Through Directive 085, the Province of Alberta has signaled that oil sands operators must improve and accelerate the methods by which they deal with FFT production, storage and treatment. This thesis aims to develop an enhanced method to forecast FFT production based on specific ore characteristics. A mass relationship and mathematical model to modify the Forecasting Tailings Model (FTM) by using fines and clay boundaries, as the two main indicators in FFT accumulation, has been developed. The modified FTM has been applied on representative block model data from an operating oil sands mining venture. An attempt has been made to identify order-of-magnitude associated tailings treatment costs, and to improve financial performance by not processing materials that have ultimate ore processing and tailings storage and treatment costs in excess of the value of bitumen they produce. The results on the real case study show that there is a 53% reduction in total tailings accumulations over the mine life by selectively processing only lower tailings generating materials through eliminating 15% of total mined ore materials with higher potential of fluid fines inventory. This significant result will assess the impact of Directive 082 on mining project economic and environmental performance towards the sustainable development of mining projects.

Karst hazard analysis towards the development of predictive karst models for southern Ontario

An investigation into karst hazard in southern Ontario has been undertaken with the intention of leading to the development of predictive karst models for this region. The reason these are not currently feasible is a lack of sufficient karst data, though this is not entirely due to the lack of karst features. Geophysical data was collected at Lake on the Mountain, Ontario as part of this karst investigation. This data was collected in order to validate the long-standing hypothesis that Lake on the Mountain was formed from a sinkhole collapse. Sub-bottom acoustic profiling data was collected in order to image the lake bottom sediments and bedrock. Vertical bedrock features interpreted as solutionally enlarged fractures were taken as evidence for karst processes on the lake bottom. Additionally, the bedrock topography shows a narrower and more elongated basin than was previously identified, and this also lies parallel to a mapped fault system in the area. This suggests that Lake on the Mountain was formed over a fault zone which also supports the sinkhole hypothesis as it would provide groundwater pathways for karst dissolution to occur. Previous sediment cores suggest that Lake on the Mountain would have formed at some point during the Wisconsinan glaciation with glacial meltwater and glacial loading as potential contributing factors to sinkhole development. A probabilistic karst model for the state of Kentucky, USA, has been generated using the Weights of Evidence method. This model is presented as an example of the predictive capabilities of these kind of data-driven modelling techniques and to show how such models could be applied to karst in Ontario. The model was able to classify 70% of the validation dataset correctly while minimizing false positive identifications. This is moderately successful and could stand to be improved. Finally, suggestions to improving the current karst model of southern Ontario are suggested with the goal of increasing investigation into karst in Ontario and streamlining the reporting system for sinkholes, caves, and other karst features so as to improve the current Ontario karst database.

Refractometry Studies of the Optical Properties of Polymer Films and the Development of Polymer Coated Refractive Index Sensors

Sensors for real-time monitoring of environmental contaminants are essential for protecting ecosystems and human health. Refractive index sensing is a non-selective technique that can be used to measure almost any analyte. Miniaturized refractive index sensors, such as silicon-on-insulator (SOI) microring resonators are one possible platform, but require coatings selective to the analytes of interest. A homemade prism refractometer is reported and used to characterize the interactions between polymer films and liquid or vapour-phase analytes. A camera was used to capture both Fresnel reflection and total internal reflection within the prism. For thin-films (d = 10 μm - 100 μm), interference fringes were also observed. Fourier analysis of the interferogram allowed for simultaneous extraction of the average refractive index and film thickness with accuracies of ∆n = 1-7 ×10-4 and ∆d < 3-5%. The refractive indices of 29 common organic solvents as well as aqueous solutions of sodium chloride, sucrose, ethylene glycol, glycerol, and dimethylsulfoxide were measured at λ = 1550 nm. These measurements will be useful for future calibrations of near-infrared refractive index sensors. A mathematical model is presented, where the concentration of analyte adsorbed in a film can be calculated from the refractive index and thickness changes during uptake. This model can be used with Fickian diffusion models to measure the diffusion coefficients through the bulk film and at the film-substrate interface. The diffusion of water and other organic solvents into SU-8 epoxy was explored using refractometry and the diffusion coefficient of water into SU-8 is presented. Exposure of soft baked SU-8 films to acetone, acetonitrile and methanol resulted in rapid delamination. The diffusion of volatile organic compound (VOC) vapours into polydimethylsiloxane and polydimethyl-co-polydiphenylsiloxane polymers was also studied using refractometry. Diffusion and partition coefficients are reported for several analytes. As a model system, polydimethyl-co-diphenylsiloxane films were coated onto SOI microring resonators. After the development of data acquisition software, coated devices were exposed to VOCs and the refractive index response was assessed. More studies with other polymers are required to test the viability of this platform for environmental sensing applications.