Fracture of materials undergoing solid-solid phase transformation

A large number of technologically important materials undergo solid-solid phase transformations. Examples range from ferroelectrics (transducers and memory devices), zirconia (Thermal Barrier Coatings) to nickel superalloys and (lithium) iron phosphate (Li-ion batteries). These transformations involve a change in the crystal structure either through diffusion of species or local rearrangement of atoms. This change of crystal structure leads to a macroscopic change of shape or volume or both and results in internal stresses during the transformation. In certain situations this stress field gives rise to cracks (tin, iron phosphate etc.) which continue to propagate as the transformation front traverses the material. In other materials the transformation modifies the stress field around cracks and effects crack growth behavior (zirconia, ferroelectrics). These observations serve as our motivation to study cracks in solids undergoing phase transformations. Understanding these effects will help in improving the mechanical reliability of the devices employing these materials.

In this thesis we present work on two problems concerning the interplay between cracks and phase transformations. First, we consider the directional growth of a set of parallel edge cracks due to a solid-solid transformation. We conclude from our analysis that phase transformations can lead to formation of parallel edge cracks when the transformation strain satisfies certain conditions and the resulting cracks grow all the way till their tips cross over the phase boundary. Moreover the cracks continue to grow as the phase boundary traverses into the interior of the body at a uniform spacing without any instabilities. There exists an optimal value for the spacing between the cracks. We ascertain these conclusion by performing numerical simulations using finite elements.

Second, we model the effect of the semiconducting nature and dopants on cracks in ferroelectric perovskite materials, particularly barium titanate. Traditional approaches to model fracture in these materials have treated them as insulators. In reality, they are wide bandgap semiconductors with oxygen vacancies and trace impurities acting as dopants. We incorporate the space charge arising due the semiconducting effect and dopant ionization in a phase field model for the ferroelectric. We derive the governing equations by invoking the dissipation inequality over a ferroelectric domain containing a crack. This approach also yields the driving force acting on the crack. Our phase field simulations of polarization domain evolution around a crack show the accumulation of electronic charge on the crack surface making it more permeable than was previously believed so, as seen in recent experiments. We also discuss the effect the space charge has on domain formation and the crack driving force.

Statistical and econometric analysis of the treatment of HIV/AIDS

The epidemic of HIV/AIDS in the United States is constantly changing and evolving, starting from patient zero to now an estimated 650,000 to 900,000 Americans infected. The nature and course of HIV changed dramatically with the introduction of antiretrovirals. This discourse examines many different facets of HIV from the beginning where there wasn't any treatment for HIV until the present era of highly active antiretroviral therapy (HAART). By utilizing statistical analysis of clinical data, this paper examines where we were, where we are and projections as to where treatment of HIV/AIDS is headed.

Chapter Two describes the datasets that were used for the analyses. The primary database utilized was collected by myself from an outpatient HIV clinic. The data included dates from 1984 until the present. The second database was from the Multicenter AIDS Cohort Study (MACS) public dataset. The data from the MACS cover the time between 1984 and October 1992. Comparisons are made between both datasets.

Chapter Three discusses where we were. Before the first anti-HIV drugs (called antiretrovirals) were approved, there was no treatment to slow the progression of HIV. The first generation of antiretrovirals, reverse transcriptase inhibitors such as AZT (zidovudine), DDI (didanosine), DDC (zalcitabine), and D4T (stavudine) provided the first treatment for HIV. The first clinical trials showed that these antiretrovirals had a significant impact on increasing patient survival. The trials also showed that patients on these drugs had increased CD4+ T cell counts. Chapter Three examines the distributions of CD4 T cell counts. The results show that the estimated distributions of CD4 T cell counts are distinctly non-Gaussian. Thus distributional assumptions regarding CD4 T cell counts must be taken, into account when performing analyses with this marker. The results also show the estimated CD4 T cell distributions for each disease stage: asymptomatic, symptomatic and AIDS are non-Gaussian. Interestingly, the distribution of CD4 T cell counts for the asymptomatic period is significantly below that of the CD4 T cell distribution for the uninfected population suggesting that even in patients with no outward symptoms of HIV infection, there exists high levels of immunosuppression.

Chapter Four discusses where we are at present. HIV quickly grew resistant to reverse transcriptase inhibitors which were given sequentially as mono or dual therapy. As resistance grew, the positive effects of the reverse transcriptase inhibitors on CD4 T cell counts and survival dissipated. As the old era faded a new era characterized by a new class of drugs and new technology changed the way that we treat HIV-infected patients. Viral load assays were able to quantify the levels of HIV RNA in the blood. By quantifying the viral load, one now had a faster, more direct way to test antiretroviral regimen efficacy. Protease inhibitors, which attacked a different region of HIV than reverse transcriptase inhibitors, when used in combination with other antiretroviral agents were found to dramatically and significantly reduce the HIV RNA levels in the blood. Patients also experienced significant increases in CD4 T cell counts. For the first time in the epidemic, there was hope. It was hypothesized that with HAART, viral levels could be kept so low that the immune system as measured by CD4 T cell counts would be able to recover. If these viral levels could be kept low enough, it would be possible for the immune system to eradicate the virus. The hypothesis of immune reconstitution, that is bringing CD4 T cell counts up to levels seen in uninfected patients, is tested in Chapter Four. It was found that for these patients, there was not enough of a CD4 T cell increase to be consistent with the hypothesis of immune reconstitution.

In Chapter Five, the effectiveness of long-term HAART is analyzed. Survival analysis was conducted on 213 patients on long-term HAART. The primary endpoint was presence of an AIDS defining illness. A high level of clinical failure, or progression to an endpoint, was found.

Chapter Six yields insights into where we are going. New technology such as viral genotypic testing, that looks at the genetic structure of HIV and determines where mutations have occurred, has shown that HIV is capable of producing resistance mutations that confer multiple drug resistance. This section looks at resistance issues and speculates, ceterus parabis, where the state of HIV is going. This section first addresses viral genotype and the correlates of viral load and disease progression. A second analysis looks at patients who have failed their primary attempts at HAART and subsequent salvage therapy. It was found that salvage regimens, efforts to control viral replication through the administration of different combinations of antiretrovirals, were not effective in 90 percent of the population in controlling viral replication. Thus, primary attempts at therapy offer the best change of viral suppression and delay of disease progression. Documentation of transmission of drug-resistant virus suggests that the public health crisis of HIV is far from over. Drug resistant HIV can sustain the epidemic and hamper our efforts to treat HIV infection. The data presented suggest that the decrease in the morbidity and mortality due to HIV/AIDS is transient. Deaths due to HIV will increase and public health officials must prepare for this eventuality unless new treatments become available. These results also underscore the importance of the vaccine effort.

The final chapter looks at the economic issues related to HIV. The direct and indirect costs of treating HIV/AIDS are very high. For the first time in the epidemic, there exists treatment that can actually slow disease progression. The direct costs for HAART are estimated. It is estimated that the direct lifetime costs for treating each HIV infected patient with HAART is between $353,000 to $598,000 depending on how long HAART prolongs life. If one looks at the incremental cost per year of life saved it is only $101,000. This is comparable with the incremental costs per year of life saved from coronary artery bypass surgery.

Policy makers need to be aware that although HAART can delay disease progression, it is not a cure and HIV is not over. The results presented here suggest that the decreases in the morbidity and mortality due to HIV are transient. Policymakers need to be prepared for the eventual increase in AIDS incidence and mortality. Costs associated with HIV/AIDS are also projected to increase. The cost savings seen recently have been from the dramatic decreases in the incidence of AIDS defining opportunistic infections. As patients who have been on HAART the longest start to progress to AIDS, policymakers and insurance companies will find that the cost of treating HIV/AIDS will increase.

How far from Jerusalem? Tropical customs and the question of race in the Book of John Mandeville

The Book of John Mandeville, while ostensibly a pilgrimage guide documenting an English knight’s journey into the East, is an ideal text in which to study the developing concept of race in the European Middle Ages. The Mandeville-author’s sense of place and morality are inextricably linked to each other: Jerusalem is the center of his world, which necessarily forces Africa and Asia to occupy the spiritual periphery. Most inhabitants of Mandeville’s landscapes are not monsters in the physical sense, but at once startlingly human and irreconcilably alien in their customs. Their religious heresies, disordered sexual appetites, and monstrous acts of cannibalism label them as fallen state of the European Christian self. Mandeville’s monstrosities lie not in the fantastical, but the disturbingly familiar, coupling recognizable humans with a miscarriage of natural law. In using real people to illustrate the moral degeneracy of the tropics, Mandeville’s ethnography helps shed light on the missing link between medieval monsters and modern race theory.

Effect of pressure on mechanical behavior of filled elastomers

The Young's modulus, stress-strain curves, and failure properties of glass bead-filled EPDM vulcanizates were studied under superposed hydrostatic pressure. The glass bead-filled EPDM was employed as a representation of composite systems, and the hydrostatic pressure controls the filler-elastomer separation under deformation. This separation shows up as a volume change of the system, and its infuence is reflected in the mechanical behavior as a reinforcing effect of variable degree.

The strain energy stored in the composite system in simple tension was calculated by introducing a model which is described as a cylindrical block of elastomer with two half spheres of filler on each end with their centers on the axis of the cylinder. In the derivation of the strain energy, assumptions were made to obtain the strain distribution in the model, and strain energy-strain relation for the elastomer was also assumed. The derivation was carried out for the case of no filler-elastomer separation and was modified to include the case of filler-elastomer separation.

The resulting strain energy, as a function of stretch ratio and volume of the system, was used to obtain stress-strain curves and volume change-strain curves of composite systems under superposed hydrostatic pressure.

Changes in the force and the lateral dimension of a ring specimen were measured as it was stretched axially under a superposed hydrostatic pressure in order to calculate the mechanical properties mentioned above. A tensile tester was used which is capable of sealing the whole system to carry out a measurement under pressure. A thickness measuring device, based on the Hall effect, was built for the measurement of changes in the lateral dimension of a specimen.

The theoretical and experimental results of Young's modulus and stress-strain curves were compared and showed fairly good agreement.

The failure data were discussed in terms of failure surfaces, and it was concluded that a failure surface of the glass-bead-filled EPDM consists of two cones.

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution.

A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation.

A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule.

Heterogeneous transformation of δ-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA.

The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

A study of the proposed Diamond Creek Reservoir

Politically the Colorado river is an interstate as well as an international stream. Physically the basin divides itself distinctly into three sections. The upper section from head waters to the mouth of San Juan comprises about 40 percent of the total of the basin and affords about 87 percent of the total runoff, or an average of about 15 000 000 acre feet per annum. High mountains and cold weather are found in this section. The middle section from the mouth of San Juan to the mouth of the Williams comprises about 35 percent of the total area of the basin and supplies about 7 percent of the annual runoff. Narrow canyons and mild weather prevail in this section. The lower third of the basin is composed of mainly hot arid plains of low altitude. It comprises some 25 percent of the total area of the basin and furnishes about 6 percent of the average annual runoff.

The proposed Diamond Creek reservoir is located in the middle section and is wholly within the boundary of Arizona. The site is at the mouth of Diamond Creek and is only 16 m. from Beach Spring, a station on the Santa Fe railroad. It is solely a power project with a limited storage capacity. The dam which creats the reservoir is of the gravity type to be constructed across the river. The walls and foundation are of granite. For a dam of 290 feet in height, the back water will be about 25 m. up the river.

The power house will be placed right below the dam perpendicular to the axis of the river. It is entirely a concrete structure. The power installation would consist of eighteen 37 500 H.P. vertical, variable head turbines, directly connected to 28 000 kwa. 110 000 v. 3 phase, 60 cycle generators with necessary switching and auxiliary apparatus. Each unit is to be fed by a separate penstock wholly embedded into the masonry.

Concerning the power market, the main electric transmission lines would extend to Prescott, Phoenix, Mesa, Florence etc. The mining regions of the mountains of Arizona would be the most adequate market. The demand of power in the above named places might not be large at present. It will, from the observation of the writer, rapidly increase with the wonderful advancement of all kinds of industrial development.

All these things being comparatively feasible, there is one difficult problem: that is the silt. At the Diamond Creek dam site the average annual silt discharge is about 82 650 acre feet. The geographical conditions, however, will not permit silt deposites right in the reservoir. So this design will be made under the assumption given in Section 4.

The silt condition and the change of lower course of the Colorado are much like those of the Yellow River in China. But one thing is different. On the Colorado most of the canyon walls are of granite, while those on the Yellow are of alluvial loess: so it is very hard, if not impossible, to get a favorable dam site on the lower part. As a visitor to this country, I should like to see the full development of the Colorado: but how about THE YELLOW!

Studies on photoblastic germination in lettuce seed

It was shown, with the aid of osmotic inhibition of germination, that the action of the far-red-absorbing form of phytochrome (Pf) in promoting germination can be completed even if the seed is held under conditions where germination is not possible. An effect of the continuing action of Pf beyond the point of complete germination promotion was demonstrated by enhancement of germination rate after removal of the osmotically active solute.

Previous reports that the rate of growth in water of seeds freed from the expansion-restricting endosperm is independent of the state of phytochrome were confirmed. However, a marked, phytochrome-mediated enhancement of the growth potential of such seeds was demonstrated through restricting water uptake by incubation in an osmoticum.

An experimental system, utilizing the appearance of a geotropic curvature in the radicle of the excised axial portion of the seed, was developed for more detailed studies of the phytochrome-enhanced growth potential. It was possible to demonstrate the light effect in water as well as in osmotica; this apparently is not possible with de-endospermed entire seeds. As in intact seeds, the effect of the continuing action of Pf is to enhance the rate of the response. Secretion of a chemical inhibitor of growth by the endosperm as a possible mechanism of induction of light sensitivity has been ruled out.

The phytochrome-dependent rate of appearance of geotropic curvature in osmotica is paralleled in time by a similar dependence of the rate of early extension growth of the embryonic axis. Only the first small increment of growth is a differentially responsive to red (R) and far-red (F); the rate of later increase in length is independent of the light regime.

It was shown that the high concentrations of gibberellic acid required for germination promotion in the intact seed are due at least in part to a diffusion barrier in the endosperm, and that the occasional reports in the literature of the ineffectiveness of kinetin are probably due to the same phenomenon. It was shown that gibberellin, like red light, enhances the growth potential of the axis, but kinetin does not. The difference in rates of response obtained after R-irradiation or gibberellin treatment, together with other results reported in the literature, strongly suggests that gibberellic acid and red light promote germination by different means. The idea that kinetin promotes germination by yet another mechanism, probably operating in the cotyledons, was supported through two different experimental approaches.

The phenomenon of temperature-dependent dark germination was examined in detail, using a wide range of both temperatures and incubation times. With the aid of the half-seed system, it was demonstrated that the promotive effect of low temperature on germination could not be due to a low optimum temperature for early growth of the radicle, since the rate of that process increased with increasing temperature, up to the highest temperature used.

It was shown that phytochrome does not function at high temperatures. This fact is of considerable importance in interpreting the phenomenon of thermodormancy, since in the literature only a small part of the effect of high temperature has been ascribed to an effect on phytochrome, and at that, only to an acceleration of dark reversion of Pf to the red-absorbing form of phytochrome (Pr). Partial denaturation of phytochrome may also make some contribution.

It was shown that the germination-promoting effect of low temperature depends on the presence of Pf, and concluded that low temperatures act by delaying or preventing transformation of Pf. Support for the assumption that Pf, not Pr, is the active form of phytochrome in lettuce seeds was drawn from the same evidence.

Attempts to stimulate germination by repeated irradiation with F over relatively prolonged incubation times resulted in failure, as have similar attempts reported in the literature. However, an enhancement of growth potential in the half-seed system by the maintenance of a small amount of Pf over long periods at ordinary temperatures by repeated irradiation with F was demonstrated.

It was observed that cold storage of the dry seed prevents or delays loss of dark dormancy during post-harvest storage. No change in the response of the half-seed in osmoticum to R and F was observed in seeds that has lost dark dormancy; that is, no internal change took place to measurably increase the growth potential of the embryonic axis. This suggests that the endosperm is the seat of changes responsible for after-ripening of photoblastic lettuce seed.

Measurements of mantle velocities of P waves with a large array

A large array has been used to investigate the P-wave velocity structure of the lower mantle. Linear array processing methods are reviewed and a method of nonlinear processing is presented. Phase velocities, travel times, and relative amplitudes of P waves have been measured with the large array at the Tonto Forest Seismological Observatory in Arizona for 125 earthquakes in the distance range of 30 to 100 degrees. Various models are assumed for the upper 771 km of the mantle and the Wiechert-Herglotz method applied to the phase velocity data to obtain a velocity depth structure for the lower mantle. The phase velocity data indicates the presence of a second-order discontinuity at a depth of 840 km, another at 1150 km, and less pronounced discontinuities at 1320, 1700 and 1950 km. Phase velocities beyond 85 degrees are interpreted in terms of a triplication of the phase velocity curve, and this results in a zone of almost constant velocity between depths of 2670 and 2800 km. Because of the uncertainty in the upper mantle assumptions, a final model cannot be proposed, but it appears that the lower mantle is more complicated than the standard models and there is good evidence for second-order discontinuities below a depth of 1000 km. A tentative lower bound of 2881 km can be placed on the depth to the core. The importance of checking the calculated velocity structure against independently measured travel times is pointed out. Comparisons are also made with observed PcP times and the agreement is good. The method of using measured values of the rate of change of amplitude with distances shows promising results.