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In many natural systems aqueous geochemical conditions dictate the reaction pathways of organic compounds. Geologic settings that span wide ranges in temperature, pressure, and composition vastly alter relative reaction rates and resulting organic abundances. The dependence of organic reactions on these variables contributes to planetary-scale nutrient cycling, and suggests that

In many natural systems aqueous geochemical conditions dictate the reaction pathways of organic compounds. Geologic settings that span wide ranges in temperature, pressure, and composition vastly alter relative reaction rates and resulting organic abundances. The dependence of organic reactions on these variables contributes to planetary-scale nutrient cycling, and suggests that relative abundances of organic compounds can reveal information about inaccessible geologic environments, whether from the terrestrial subsurface, remote planetary settings, or even the distant past (if organic abundances are well preserved). Despite their relevance to planetary modeling and exploration, organic reactions remain poorly characterized under geochemically relevant conditions, especially in terms of their reaction kinetics, mechanisms, and equilibria.

In order to better understand organic transformations in natural systems, the reactivities of oxygen- and nitrogen-bearing organic functional groups were investigated under experimental hydrothermal conditions, at 250°C and 40 bar. The model compounds benzylamine and α-methylbenzylamine were used as analogs to environmentally relevant amines, ultimately elucidating two dominant deamination mechanisms for benzylamine, SN1 and SN2, and a single SN1 mechanism for deamination of α-methylbenzylamine. The presence of unimolecular and bimolecular mechanisms has implications for temperature dependent kinetics, indicating that Arrhenius rate extrapolation is currently unreliable for deamination.

Hydrothermal experiments with benzyl alcohol, benzylamine, dibenzylamine, or tribenzylamine as the starting material indicate that substitution reactions between these compounds (and others) are reversible and approach metastable equilibrium after 72 hours. These findings suggest that relative ratios of organic compounds capable of substitution reactions could be targeted as tracers of inaccessible geochemical conditions.

Metastable equilibria for organic reactions were investigated in a natural low-temperature serpentinizing continental system. Serpentinization is a water-rock reaction which generates hyperalkaline, reducing conditions. Thermodynamic calculations were performed for reactions between dissolved inorganic carbon and hydrogen to produce methane, formate, and acetate. Quantifying conditions that satisfy equilibrium for these reactions allows subsurface conditions to be predicted. These calculations also lead to hypotheses regarding active microbial processes during serpentinization.
ContributorsRobinson, Kirtland J (Author) / Shock, Everett L (Thesis advisor) / Herckes, Pierre (Committee member) / Hartnett, Hilairy E (Committee member) / Anbar, Ariel D (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Many industries require workers in warehouse and stockroom environments to perform frequent lifting tasks. Over time these repeated tasks can lead to excess strain on the worker's body and reduced productivity. This project seeks to develop an exoskeletal wrist fixture to be used in conjunction with a powered exoskeleton arm

Many industries require workers in warehouse and stockroom environments to perform frequent lifting tasks. Over time these repeated tasks can lead to excess strain on the worker's body and reduced productivity. This project seeks to develop an exoskeletal wrist fixture to be used in conjunction with a powered exoskeleton arm to aid workers performing box lifting types of tasks. Existing products aimed at improving worker comfort and productivity typically employ either fully powered exoskeleton suits or utilize minimally powered spring arms and/or fixtures. These designs either reduce stress to the user's body through powered arms and grippers operated via handheld controls which have limited functionality, or they use a more minimal setup that reduces some load, but exposes the user's hands and wrists to injury by directing support to the forearm. The design proposed here seeks to strike a balance between size, weight, and power requirements and also proposes a novel wrist exoskeleton design which minimizes stress on the user's wrists by directly interfacing with the object to be picked up. The design of the wrist exoskeleton was approached through initially selecting degrees of freedom and a ROM (range of motion) to accommodate. Feel and functionality were improved through an iterative prototyping process which yielded two primary designs. A novel "clip-in" method was proposed to allow the user to easily attach and detach from the exoskeleton. Designs utilized a contact surface intended to be used with dry fibrillary adhesives to maximize exoskeleton grip. Two final designs, which used two pivots in opposite kinematic order, were constructed and tested to determine the best kinematic layout. The best design had two prototypes created to be worn with passive test arms that attached to the user though a specially designed belt.
ContributorsGreason, Kenneth Berend (Author) / Sugar, Thomas (Thesis director) / Holgate, Matthew (Committee member) / Mechanical and Aerospace Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
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Description
For the past two decades, advanced Limb Gait Simulators and Exoskeletons have been developed to improve walking rehabilitation. A Limb Gait Simulator is used to analyze the human step cycle and/or assist a user walking on a treadmill. Most modern limb gait simulators, such as ALEX, have proven themselves effective

For the past two decades, advanced Limb Gait Simulators and Exoskeletons have been developed to improve walking rehabilitation. A Limb Gait Simulator is used to analyze the human step cycle and/or assist a user walking on a treadmill. Most modern limb gait simulators, such as ALEX, have proven themselves effective and reliable through their usage of motors, springs, cables, elastics, pneumatics and reaction loads. These mechanisms apply internal forces and reaction loads to the body. On the other hand, external forces are those caused by an external agent outside the system such as air, water, or magnets. A design for an exoskeleton using external forces has seldom been attempted by researchers. This thesis project focuses on the development of a Limb Gait Simulator based on a Pure External Force and has proven its effectiveness in generating torque on the human leg. The external force is generated through air propulsion using an Electric Ducted Fan (EDF) motor. Such a motor is typically used for remote control airplanes, but their applications can go beyond this. The objective of this research is to generate torque on the human leg through the control of the EDF engines thrust and the opening/closing of the reverse thruster flaps. This device qualifies as "assist as needed"; the user is entirely in control of how much assistance he or she may want. Static thrust values for the EDF engine are recorded using a thrust test stand. The product of the thrust (N) and the distance on the thigh (m) is the resulting torque. With the motor running at maximum RPM, the highest torque value reached was that of 3.93 (Nm). The motor EDF motor is powered by a 6S 5000 mAh LiPo battery. This torque value could be increased with the usage of a second battery connected in series, but this comes at a price. The designed limb gait simulator demonstrates that external forces, such as air, could have potential in the development of future rehabilitation devices.
ContributorsToulouse, Tanguy Nathan (Author) / Sugar, Thomas (Thesis director) / Artemiadis, Panagiotis (Committee member) / Mechanical and Aerospace Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12