Investigation of gas engine driven heat pump systems

Heat pumps are becoming increasingly popular, but poor electricity generating efficiency limits the potential energy savings of electrically powered units. Thus the work reported in this thesis concerns the development of a range of gas engine driven heat pumps for industrial and commercial heating applications, which recover heat from the prime mover, normally rejected to waste. Despite the convenience of using proprietary engine heat recovery packages, investigations have highlighted the necessity to ensure the engine and the heat recovery equipment are compatible. A problem common •to all air source heat pumps is the formation of frost on the evaporator, which must be removed periodically, with the expenditure of energy, to ensure the continued operation of the plant. An original fluidised bed defrosting mechanism is proposed, which prevents the build-up of this frost, and also improves system performance. Criticisms have been levelled against the rotary sliding vane compressor, in particular the effects of lubrication, which is essential. This thesis compares the rotary sliding vane compressor with other machines, and concludes that many of these criticisms are unfounded. A confidential market survey indicates an increasing demand for heat pumps up to and including 1990, and the technical support needed to penetrate this market is presented. Such support includes the development of a range of modular gas engine driven heat pumps, and a computer aided design for the selection of the optimum units. A case study of a gas engine driven heat pump for a swimming pool application which provided valuable experience is included.

Electrodeposition on magnesium alloy diecasting

Magnesium alloy diecasting AZ91CC, AZ61CC', AZ91HC and AZ71HC were electroplated using different pretreatment sequences which incorporated conventional zincate immersion processes. Satisfactory peel adhesion in excess of 7. 7 KNm -1 was achieved on AZ61CC using a sequence which was designated Canning. The comparatively low adhesion achieved on the AZ91HC was due to its poor surface quality as cast. Growth of deposits was monitored using a strip-and-analysis technique and the morphology of the various deposits were studied using scanning electron microscopy. Different pretreatment sequences resulted in different surface responses for the alloys but all alloys behaved in a similar manner in a particular sequence with regard to potential time-curves and the rate of zinc deposition. The role of fluoride in both the second stage solution and zinc immersion stages of the Canning pretreatment sequence was studied using techniques listed above and Auger electron spectroscopy. Complete coverage of the magnesium alloy surface with immersion zinc was achieved when fluoride was absent from the zincating solution. However, a zero adhesion value was indicated in both thermal cycling and peel tests. The presence of fluoride in the immersion zinc solution suppressed the rate of zinc deposition and affected the time taken to reach equilibrium during potential-time determinations. A mechanism is suggested to explain the significance of fluoride additions to the processing solutions. pH and composition of the zincating solution had a significant effect on the time taken to produce the step observed in the potential/time curves and hence equilibrium potential. Immersion zinc deposition occurred rapidly at first but then changed to a lower uniform rate at a point corresponding approximately to the step in the potential/time curve. Although the minimun levels of adhesion, using the Canning sequence, varied from 7.72 KNm-1 for alloy AZ61CC to 1.54 KNm-1 for alloy AZ91HC, all the alloys revealed ductile failure characteristics in the surface layer of the substrate after peel testing. Plated magnesium alloys exhibited good corrosion resistance when appropriately pretreated and overplated with adequate nickel chromium coatings. The immersion zinc layer was not preferentially attacked when pits penetrated to the coating/substrate interface. Hemispherical pits formed and attack on the substrate was severe. Of the pretreatment sequences investigated, the Canning one was the most premising with respect to peel adhesion and corrosion behaviour.

Steric stabilization and dissolution characteristics of aqueous suspensions of pharmaceutical interest

The adsorption of two qroups of nonionic surface active agents and a series of hiqh molecular weiqht hydrophilic polymer fractions onto a polystyrene latex and a drug substance diloxanide furoate B.P. has been investigated. The presence of pores within the drug surface has been demonstrated and this is shown to increase the adsorption of low molecular weight polymer species. Differences in the maximum amount of polymer adsorbed at both solid-solution interfaces have been ascribed to the different hydrophobicities of the surface as determined by contact angle measurements. Adsorbed layer thicknesses of polymer on polystyrene latex have been determined by three techniques: microelectrophoresis, intensity fluctuation spectroscopy and by viscometric means. These results, in combination with adsorption data, were used to interpret the configuration of the adsorbed polymer molecules at the interface. The type of druq suspension produced on adsorbing the different polymers in the absence of electrostatic stabilization was correlated with theoretical prediuctions of suspension characteristics deduced from potential energy diagrams, The agreement was good for the adsorption of short chain length surfactants, but for the polyvinylalcohols, discrepancies were found between experiment and theory. This was attributed to the inappropriate use of a mean segment density approximation within the adsorbed layer to calculate attractive potentials between particles. A maximum in the redispersibility values for suspensions coated with adsorbed nonylphenylethoxylates was attributed to "partial static stabilization" of the particles in conjunction with the attractive forces operating in the sediment between bare surface patches on neighbouring particles. No significant change in the dissolution of the drug was observed when nonylphenylethoxylates were adsorbed due to desorption upon contact with the dissolution medium. Pluronic F68 and all the polyvinylalcohol fractions caused a reduction in the dissolution rate which is explained by the decreased diffusion of drug' through the adsorbed polymer layer.

The effect of certain hydrophilic polymers on suspension stability

The adsorption of nonionic surface active agents of polyoxyethylene glycol monoethers of n hexadecanols on polystyrene latex and nonionic cellulose polymers of hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methylcellulose on polystyrene latex and ibuprofen drug particles have been studied. The adsorbed layer thicknesses were determined by means of microelectrophoretic and viscometric methods. The conformation of the adsorbed molecules at the solid-liquid interface was deduced from the molecular areas and the adsorbed layer thicknesses. Comparison of the adsorption results obtained from polystyrene latex and ibuprofen particles was made to explain the conformation difference between these two adsorbates. Sedimentation volumes and redispersibility values were the main criteria used to evaluate suspension stability. At low concentrations of surface active agents, hard caked suspensions were found, probably due to the attraction between the uncoated areas or, the mutual adsorption of the adsorbed molecules on the bare surface of the particles in the sediment. At high concentrations of hydroxypropyl cellulose and hydroxypropyl methylcellulose, heavily caked sediments were attributed to network structure formation by the adsorbed molecules. An attempt was made to relate the characteristics of the suspensions to the potential energy of interaction curves. Generally, the agreement between theory and experiment was good, but for hydroxyethyl cellulose-ibuprofen systems discrepancies were found. Experimental studies showed that hydroxyethyl cellulose flocculated polystyrene latex over a rather wide range of concentrations; similarly, hydroxyethyl cellulose-ibuprofen suspensions were also flocculated. Therefore, it ls suggested that a term to account for flocculation energy of the polymer should be added to the total energy of interaction. A rheometric method was employed to study the flocculation energy of the polymer.

The intermediate pyrolysis and catalytic steam reforming of brewers spent grain

Brewers spent grain (BSG) is a widely available feedstock representing approximately 85% of the total by-products generated in the brewing industry. This is currently either disposed of to landfill or used as cattle feed due to its high protein content. BSG has received little or no attention as a potential energy resource, but increasing disposal costs and environmental constraints are now prompting the consideration of this. One possibility for the utilisation of BSG for energy is via intermediate pyrolysis to produce gases, vapours and chars. Intermediate pyrolysis is characterised by indirect heating in the absence of oxygen for short solids residence times of a few minutes, at temperatures of 350-450 °C. In the present work BSG has been characterised by chemical, proximate, ultimate and thermo-gravimetric analysis. Intermediate pyrolysis of BSG at 450 °C was carried out using a twin coaxial screw reactor known as Pyroformer to give yields of char 29%, 51% of bio-oil and 19% of permanent gases. The bio-oil liquid was found to separate in to an aqueous phase and organic phase. The organic phase contained viscous compounds that could age over time leading to solid tars that can present problems in CHP application. The quality of the pyrolysis vapour products before quenching can be upgraded to achieve much improved suitability as a fuel by downstream catalytic reforming. A Bench Scale batch pyrolysis reactor has then been used to pyrolyse small samples of BSG under a range of conditions of heating rate and temperature simulating the Pyroformer. A small catalytic reformer has been added downstream of the reactor in which the pyrolysis vapours can be further cracked and reformed. A commercial reforming nickel catalyst was used at 500, 750 and 850 °C at a space velocity about 10,000 L/h with and without the addition of steam. Results are presented for the properties of BSG, and the products of the pyrolysis process both with and without catalytic post-processing. Results indicate that catalytic reforming produced a significant increase in permanent gases mainly (H2 and CO) with H2 content exceeding 50 vol% at higher reforming temperatures. Bio-oil yield decreased significantly as reforming temperature increased with char remaining the same as pyrolysis condition remained unchanged. The process shows an increase in heating value for the product gas ranging between 10.8-25.2 MJ/m as reforming temperature increased. © 2012 Elsevier B.V. All rights reserved.

Molecular dynamics simulation of brittle fracture in silicon

The fracture process involves converting potential energy from a strained body into surface energy, thermal energy, and the energy needed to create lattice defects. In dynamic fracture, energy is also initially converted into kinetic energy. This paper uses molecular dynamics (MD) to simulate brittle frcture in silicon and determine how energy is converted from potential energy (strain energy) into other forms.

Ab initio quantum chemical studies on neutral-radical reactions of ethynyl (C2H) and cyano (CN) with unsaturated hydrocarbons

An Ab Initio/RRKM study of the reaction mechanism and product branching ratios of neutral-radical ethynyl (C2H) and cyano (CN) radical species with unsaturated hydrocarbons is performed. The reactions studied apply to cold conditions such as planetary atmospheres including Titan, the Interstellar Medium (ISM), icy bodies and molecular clouds. The reactions of C2H and CN additions to gaseous unsaturated hydrocarbons are an active area of study. NASA's Cassini/Huygens mission found a high concentration of C2H and CN from photolysis of ethyne (C2H2) and hydrogen cyanide (HCN), respectively, in the organic haze layers of the atmosphere of Titan. The reactions involved in the atmospheric chemistry of Titan lead to a vast array of larger, more complex intermediates and products and may also serve as a chemical model of Earth's primordial atmospheric conditions. The C2H and CN additions are rapid and exothermic, and often occur barrierlessly to various carbon sites of unsaturated hydrocarbons. The reaction mechanism is proposed on the basis of the resulting potential energy surface (PES) that includes all the possible intermediates and transition states that can occur, and all the products that lie on the surface. The B3LYP/6-311g(d,p) level of theory is employed to determine optimized electronic structures, moments of inertia, vibrational frequencies, and zero-point energy. They are followed by single point higher-level CCSD(T)/cc-vtz calculations, including extrapolations to complete basis sets (CBS) of the reactants and products. A microcanonical RRKM study predicts single-collision (zero-pressure limit) rate constants of all reaction paths on the potential energy surface, which is then used to compute the branching ratios of the products that result. These theoretical calculations are conducted either jointly or in parallel to experimental work to elucidate the chemical composition of Titan's atmosphere, the ISM, and cold celestial bodies.<.

Formation of Polycyclic Aromatic Hydrocarbons and Nitrogen Containing Polycyclic Aromatic Compounds in Titan's Atmosphere, the Interstellar Medium and Combustion

Several different mechanisms leading to the formation of (substituted) naphthalene and azanaphthalenes were examined using theoretical quantum chemical calculations. As a result, a series of novel synthetic routes to Polycyclic Aromatic Hydrocarbons (PAHs) and Nitrogen Containing Polycyclic Aromatic Compounds (N-PACs) have been proposed. On Earth, these aromatic compounds originate from incomplete combustion and are released into our environment, where they are known to be major pollutants, often with carcinogenic properties. In the atmosphere of a Saturn's moon Titan, these PAH and N-PACs are believed to play a critical role in organic haze formation, as well as acting as chemical precursors to biologically relevant molecules. The theoretical calculations were performed by employing the ab initio G3(MP2,CC)/B3LYP/6-311G** method to effectively probe the Potential Energy Surfaces (PES) relevant to the PAH and N-PAC formation. Following the construction of the PES, Rice-Ramsperger-Kassel-Markus (RRKM) theory was used to evaluate all unimolecular rate constants as a function of collision energy under single-collision conditions. Branching ratios were then evaluated by solving phenomenological rate expressions for the various product concentrations. The most viable pathways to PAH and N-PAC formation were found to be those where the initial attack by the ethynyl (C2H) or cyano (CN) radical toward a unsaturated hydrocarbon molecule led to the formation of an intermediate which could not effectively lose a hydrogen atom. It is not until ring cyclization has occurred, that hydrogen elimination leads to a closed shell product. By quenching the possibility of the initial hydrogen atom elimination, one of the most competitive processes preventing the PAH or N-PAC formation was avoided, and the PAH or N-PAC formation was allowed to proceed. It is concluded that these considerations should be taken into account when attempting to explore any other potential routes towards aromatic compounds in cold environments, such as on Titan or in the interstellar medium.

Contribuição ao estudo de treliças não lineares considerando efeitos térmicos

This work presents the numerical analysis of nonlinear trusses summited to thermomechanical actions with Finite Element Method (FEM). The proposed formulation is so-called positional FEM and it is based on the minimum potential energy theorem written according to nodal positions, instead of displacements. The study herein presented considers the effects of geometric and material nonlinearities. Related to dynamic problems, a comparison between different time integration algorithms is performed. The formulation is extended to impact problems between trusses and rigid wall, where the nodal positions are constrained considering nullpenetration condition. In addition, it is presented a thermodynamically consistent formulation, based on the first and second law of thermodynamics and the Helmholtz free-energy for analyzing dynamic problems of truss structures with thermoelastic and thermoplastic behavior. The numerical results of the proposed formulation are compared with examples found in the literature.

Age determination of sediment core NP90-52 (Table 1)

Data on glacial erosion have been compiled and synthesised using a wide range of sediment budget and sediment yield studies from the Svalbard-Barents Sea region. The data include studies ranging in timescale from 1 to 10**6 yr, and in size of drainage basin from 101 to 105 km**2. They show a clear dependence of sediment yield on the mode of glacierization. Polar glaciers erode at rates comparable to those found in Arctic fluvial basins, or about 40 t/km**-2/ yr or 0.02 mm/yr. In contrast, rates of erosion by polythermal glaciers are 800-1000 t/km**2/ yr (or ca 0.3-0.4 mm/yr), while rates from fast-flowing glaciers are slightly more than twice this: 2100 t/km**2/yr (or 1 mm/yr). Similar rates are also found for large glacierized basins like those in the southwestern parts of the Barents Sea. In contrast to the situation in fluvial basins, in which sediment yield typically decreases with increasing basin size, the tendency in glacierized basins is for erosion to be independent of basin size. In studies of sediment yield from glaciers it is sometimes difficult to distinguish between material actually dislodged from the bedrock by glaciers and material dislodged by other processes in interglacial times and simply transported to a depocenter by a glacier. Our data suggest that pulses of sediment resulting from advance of a glacier over previously-dislodged material last on the order of 10**3 yr, and result in inferred erosion rates that are approximately 25% higher than long-term average rates of glacial erosion. The maximum sediment fluxes from the large Storfjorden and Bear Island drainage basins occurred in mid-Pleistocene. The onset of this period of high sediment yield coincided with the onset of the 100 kyr glacial cycle. We presume that this was the beginning of a period of increased glacial activity, but one in which glaciers still advanced and retreated frequently. During the last two to four 100 kyr cycles, however, sediment yields appear to have decreased. This decrease may be the result of the submergence of the Barents Sea. Glacier erosion would be much higher for a subaerial Barents Sea setting than it would be for a present day subsea Barents Sea. A classical question in Quaternary Geology is whether glaciers are more erosive than rivers. We surmise that if factors such as the lithology and the available potential energy (mgh) of the precipitation falling at a given altitude, whether in liquid or solid form, are held constant, then glaciers are vastly more effective agents of erosion than rivers.

Determination of Biomolecular Interdomain Motions using Nuclear Magnetic Resonance

Biological macromolecules can rearrange interdomain orientations when binding to various partners. Interdomain dynamics serve as a molecular mechanism to guide the transitions between orientations. However, our understanding of interdomain dynamics is limited because a useful description of interdomain motions requires an estimate of the probabilities of interdomain conformations, increasing complexity of the problem.

Staphylococcal protein A (SpA) has five tandem protein-binding domains and four interdomain linkers. The domains enable Staphylococcus aureus to evade the host immune system by binding to multiple host proteins including antibodies. Here, I present a study of the interdomain motions of two adjacent domains in SpA. NMR spin relaxation experiments identified a 6-residue flexible interdomain linker and interdomain motions. To quantify the anisotropy of the distribution of interdomain orientations, we measured residual dipolar couplings (RDCs) from the two domains with multiple alignments. The N-terminal domain was directly aligned by a lanthanide ion and not influenced by interdomain motions, so it acted as a reference frame to achieve motional decoupling. We also applied {\it de novo} methods to extract spatial dynamic information from RDCs and represent interdomain motions as a continuous distribution on the 3D rotational space. Significant anisotropy was observed in the distribution, indicating the motion populates some interdomain orientations more than others. Statistical thermodynamic analysis of the observed orientational distribution suggests that it is among the energetically most favorable orientational distributions for binding to antibodies. Thus, the affinity is enhanced by a pre-posed distribution of interdomain orientations while maintaining the flexibility required for function.

The protocol described above can be applied to other biological systems in general. Protein molecule calmodulin and RNA molecule trans-activation response element (TAR) also have intensive interdomain motions with relative small intradomain dynamics. Their interdomain motions were studied using our method based on published RDC data. Our results were consistent with literature results in general. The differences could be due to previous studies' use of physical models, which contain assumptions about potential energy and thus introduced non-experimental information into the interpretations.

Nonholonomically Constrained Dynamics and Optimization of Rolling Isolation Systems

Rolling Isolation Systems provide a simple and effective means for protecting components from horizontal floor vibrations. In these systems a platform rolls on four steel balls which, in turn, rest within shallow bowls. The trajectories of the balls is uniquely determined by the horizontal and rotational velocity components of the rolling platform, and thus provides nonholonomic constraints. In general, the bowls are not parabolic, so the potential energy function of this system is not quadratic. This thesis presents the application of Gauss's Principle of Least Constraint to the modeling of rolling isolation platforms. The equations of motion are described in terms of a redundant set of constrained coordinates. Coordinate accelerations are uniquely determined at any point in time via Gauss's Principle by solving a linearly constrained quadratic minimization. In the absence of any modeled damping, the equations of motion conserve energy. This mathematical model is then used to find the bowl profile that minimizes response acceleration subject to displacement constraint.

Dynamics of the Disk-Pendulum Coupled System With Vertical Excitation

This paper investigates the static and dynamic characteristics of the semi-elliptical rocking disk on which a pendulum pinned. This coupled system’s response is also analyzed analytically and numerically when a vertical harmonic excitation is applied to the bottom of the rocking disk. Lagrange’s Equation is used to derive the motion equations of the disk-pendulum coupled system. The second derivative test for the system’s potential energy shows how the location of the pendulum’s pivotal point affects the number and stability of equilibria, and the change of location presents different bifurcation diagrams for different geometries of the rocking disk. For both vertically excited and unforced cases, the coupled system shows chaos easily, but the proper chosen parameters can still help the system reach and keep the steady state. For the steady state of the vertically excited rocking disk without a pendulum, the variation of the excitation’s amplitude and frequency result in the hysteresis for the amplitude of the response. When a pendulum is pinned on the rocking disk, three major categories of steady states are presently in the numerical way.

Mechanochemistry for Active Materials and Devices

The coupling of mechanical stress fields in polymers to covalent chemistry (polymer mechanochemistry) has provided access to previously unattainable chemical reactions and polymer transformations. In the bulk, mechanochemical activation has been used as the basis for new classes of stress-responsive polymers that demonstrate stress/strain sensing, shear-induced intermolecular reactivity for molecular level remodeling and self-strengthening, and the release of acids and other small molecules that are potentially capable of triggering further chemical response. The potential utility of polymer mechanochemistry in functional materials is limited, however, by the fact that to date, all reported covalent activation in the bulk occurs in concert with plastic yield and deformation, so that the structure of the activated object is vastly different from its nascent form. Mechanochemically activated materials have thus been limited to “single use” demonstrations, rather than as multi-functional materials for structural and/or device applications. Here, we report that filled polydimethylsiloxane (PDMS) elastomers provide a robust elastic substrate into which mechanophores can be embedded and activated under conditions from which the sample regains its original shape and properties. Fabrication is straightforward and easily accessible, providing access for the first time to objects and devices that either release or reversibly activate chemical functionality over hundreds of loading cycles.

While the mechanically accelerated ring-opening reaction of spiropyran to merocyanine and associated color change provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, the magnitude of the forces necessary for activation had yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the timescale of tens of milliseconds is found to require forces of ~240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Importantly, quantifying the magnitude of forces required to activate individual spiropyran-based force-probes enables the probe behave as a “scout” of molecular forces in materials; the observed behavior of which can be extrapolated to predict the reactivity of potential mechanophores within a given material and deformation.

We subsequently translated the design platform to existing dynamic soft technologies to fabricate the first mechanochemically responsive devices; first, by remotely inducing dielectric patterning of an elastic substrate to produce assorted fluorescent patterns in concert with topological changes; and second, by adopting a soft robotic platform to produce a color change from the strains inherent to pneumatically actuated robotic motion. Shown herein, covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation into value-added, constructive covalent chemical responses. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional actuating device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the actuator in a way that might also be coupled to feedback loops that allow autonomous, self-regulation of activity.

In the future, both the specific material and the general approach should be useful in enriching the responsive functionality of soft elastomeric materials and devices. We anticipate the development of new mechanophores that, like the materials, are reversibly and repeatedly activated, expanding the capabilities of soft, active devices and further permitting dynamic control over chemical reactivity that is otherwise inaccessible, each in response to a single remote signal.

Integrated Housing Approach for Riyadh’s hot arid Climate: solutions from the desert vernacular

Thesis (Master's)--University of Washington, 2016-06