Rate and Microstructure Effects on the Dynamics of Carbon Nanotube Foams

Soft hierarchical materials often present unique functional properties that are sensitive to the geometry and organization of their micro- and nano-structural features across different lengthscales. Carbon Nanotube (CNT) foams are hierarchical materials with fibrous morphology that are known for their remarkable physical, chemical and electrical properties. Their complex microstructure has led them to exhibit intriguing mechanical responses at different length-scales and in different loading regimes. Even though these materials have been studied for mechanical behavior over the past few years, their response at high-rate finite deformations and the influence of their microstructure on bulk mechanical behavior and energy dissipative characteristics remain elusive.

In this dissertation, we study the response of aligned CNT foams at the high strain-rate regime of 10² - 10⁴ s^-1. We investigate their bulk dynamic response and the fundamental deformation mechanisms at different lengthscales, and correlate them to the microstructural characteristics of the foams. We develop an experimental platform, with which to study the mechanics of CNT foams in high-rate deformations, that includes direct measurements of the strain and transmitted forces, and allows for a full field visualization of the sample’s deformation through high-speed microscopy.

We synthesize various CNT foams (e.g., vertically aligned CNT (VACNT) foams, helical CNT foams, micro-architectured VACNT foams and VACNT foams with microscale heterogeneities) and show that the bulk functional properties of these materials are highly tunable either by tailoring their microstructure during synthesis or by designing micro-architectures that exploit the principles of structural mechanics. We also develop numerical models to describe the bulk dynamic response using multiscale mass-spring models and identify the mechanical properties at length scales that are smaller than the sample height.

The ability to control the geometry of microstructural features, and their local interactions, allows the creation of novel hierarchical materials with desired functional properties. The fundamental understanding provided by this work on the key structure-function relations that govern the bulk response of CNT foams can be extended to other fibrous, soft and hierarchical materials. The findings can be used to design materials with tailored properties for different engineering applications, like vibration damping, impact mitigation and packaging.

Nonlinear dynamics of negatively refracted light in a resonantly absorbing Bragg reflector

The evolution of nonlinear light fields traveling inside a resonantly absorbing Bragg reflector is studied by use of Maxwell-Bloch equations. Numerical results show that a pulse initially resembling a light bullet may effectively experience negative refraction and anomalous dispersion in the resonantly absorbing Bragg reflector. (c) 2007 Optical Society of America.

The impact of year-to-year changes in the weather on the seasonal dynamics of lakes

The methods currently used to monitor and model lakes were developed when weather conditions were very different to what they are today. Most are based on samples collected at weekly or fortnightly intervals and cannot quantify the effects of short-term, more extreme, variations in the weather. In this article, the author presents some examples to show the importance of developing new monitoring methods using case studies from a number of lakes in the English Lake District. The impact of year-to-year changes and short-term changes on the dynamics of of lakes are highlighted.

Discovery of viruses lysing blue-green algae in the Dneprovsk reservoirs. [Translation of: Water blooms (ed. A. V. Topachevskii) pp.171-174. Kiev, Naukova Dumka, 1968]

Viruses, which are characterised by a relative simplicity of chemical composition, are involved with all the groups of the animal and plant world. The discovery of viruses of lower organisms has special interest. Along with the already known viruses lysing bacteria and actinomycetes, viruses have been discovered in recent years which lyse algae. During investigations of water from water-bloom patches and of mud taken from zones of massive accumulation of blue-green algae in the Dneprovsk reservoirs, the authors obtained viruses lysing algae. The revealing of viruses producing lysis of blue-green algae, which one could use in the control of water-blooms, has the greatest interest. With this aim, samples of water were collected from various zones of water-bloom patches in the Kremenchug, Dneprovsk and Kukhov reservoirs. For viruses lysing algae we propose the name 'algophages'. Along with the existence of viruses of algae of the phage type, one cannot deny the possibility of the existence of viruses of another type, multiplying in the cells of algae and causing their virus illnesses.

On the population dynamics of Eudiaptomus gracilis Sars and Heterocope borealis Fischer in the Bodensee-Obersee. Part B. Eudiaptomus gracilis Sars. [Translation from: Trudy Instituta Biologii Vnutrennykh Vodnany 12(15) 170-174, 1966.]

Experimental research was conducted to study the development of eggs of Eudiaptomus gracilis Sars. The egg production was studied as well as the population dynamics. Factors like losses in the lake and through the effluent Rhine at Konstanz were considered.

A marked effect of water snails on small crustaceans. [Translation from: Anz.Ost.Akad.Wiss 10, 95-99, 1952. ]

Cases of mutual exclusion of two species of organisms in nature are known in large numbers. In the majority, they make different demands on the environ- ment which makes co-occurrence impossible. Less frequent are those cases in which a definite activity of one species prevents the occurrence of the other in the same region. An experiment was carried out n order to establish if Chydorus sphaericus can co-occur with water-snails. It emerged that a substance soluble in water which is given off by snails is responsible for the negative effect on small crustacea.

The dynamics of the fecundity of fishes, for example the roach, Rutilus rutilus (L.). [conclusions and figure/table captions only] [Translation from: Voprosy Ikhtiologii 3(1) 67-83, 1963]

The dynamics of the fecundity of roach, with emphasis on Rutilus rutilus (L.), were studied in waters in the European parts of the USSR. This translation provides conclusions, and figures and table captions only.

The Atmospheric Dynamics of Pulsar Companions

Pulsars emit radiation over an extremely wide frequency range, from radio through gamma. Recently, systems in which this radiation significantly alters the atmospheres of low-mass pulsar companions have been discovered. These systems, ranging from ones with highly anisotropic heating to those with transient X-ray emissions, represent an exciting opportunity to investigate pulsars through the changes they induce in their companions. In this work, we present both analytic and numerical work investigating these phenomena, with a particular focus on atmospheric heat transport, transient phenomena, and the possibility of deep heating via gamma rays. We find that certain classes of binary systems may explain decadal-timescale X-ray transient phenomena, as well as the formation of so-called redback companion systems. We also posit an explanation for the formation of high-eccentricity millisecond pulsars with white dwarf companions. In addition, we examine the temperature anisotropy induced by the Pulsar in its companion, and demonstrate that this may be used to infer properties of both the companion and the Pulsar wind. Finally, we explore the possibility of spontaneously generated banded winds in rapidly rotating convecting objects.

The Colorado River; a source of water and power for Los Angeles

The rapid growth and development of Los Angeles City and County has been one of the phenomena of the present age. The growth of a city from 50,600 to 576,000, an increase of over 1000% in thirty years is an unprecedented occurrence. It has given rise to a variety of problems of increasing magnitude.

Chief among these are: supply of food, water and shelter development of industry and markets, prevention and removal of downtown congestion and protection of life and property. These, of course, are the problems that any city must face. But in the case of a community which doubles its population every ten years, radical and heroic measures must often be taken.

I. The rate and mechanism of the vapor-phase reaction between water and parts-per-million concentrations of nitrogen dioxide. II. The rate and mechanism of the air oxidation of parts-per-million concentrations of nitric oxide in the presence of water vapor.

Part I

A study of the thermal reaction of water vapor and parts-per-million concentrations of nitrogen dioxide was carried out at ambient temperature and at atmospheric pressure. Nitric oxide and nitric acid vapor were the principal products. The initial rate of disappearance of nitrogen dioxide was first order with respect to water vapor and second order with respect to nitrogen dioxide. An initial third-order rate constant of 5.5 (± 0.29) x 10⁴ liter² mole^-2 sec^-1 was found at 25˚C. The rate of reaction decreased with increasing temperature. In the temperature range of 25˚C to 50˚C, an activation energy of -978 (± 20) calories was found.

The reaction did not go to completion. From measurements as the reaction approached equilibrium, the free energy of nitric acid vapor was calculated. This value was -18.58 (± 0.04) kilocalories at 25˚C.

The initial rate of reaction was unaffected by the presence of oxygen and was retarded by the presence of nitric oxide. There were no appreciable effects due to the surface of the reactor. Nitric oxide and nitrogen dioxide were monitored by gas chromatography during the reaction.

Part II

The air oxidation of nitric oxide, and the oxidation of nitric oxide in the presence of water vapor, were studied in a glass reactor at ambient temperatures and at atmospheric pressure. The concentration of nitric oxide was less than 100 parts-per-million. The concentration of nitrogen dioxide was monitored by gas chromatography during the reaction.

For the dry oxidation, the third-order rate constant was 1.46 (± 0.03) x 10⁴ liter² mole^-2 sec^-1 at 25˚C. The activation energy, obtained from measurements between 25˚C and 50˚C, was -1.197 (±0.02) kilocalories.

The presence of water vapor during the oxidation caused the formation of nitrous acid vapor when nitric oxide, nitrogen dioxide and water vapor combined. By measuring the difference between the concentrations of nitrogen dioxide during the wet and dry oxidations, the rate of formation of nitrous acid vapor was found. The third-order rate constant for the formation of nitrous acid vapor was equal to 1.5 (± 0.5) x 10⁵ liter² mole^-2 sec^-1 at 40˚C. The reaction rate did not change measurably when the temperature was increased to 50˚C. The formation of nitric acid vapor was prevented by keeping the concentration of nitrogen dioxide low.

Surface effects were appreciable for the wet tests. Below 35˚C, the rate of appearance of nitrogen dioxide increased with increasing surface. Above 40˚C, the effect of surface was small.

I. A study of the dynamics of triplet excitons in molecular crystals. II. An investigation of delayed light emission from Chlorella pyrenoidosa

I. PREAMBLE AND SCOPE

Brief introductory remarks, together with a definition of the scope of the material discussed in the thesis, are given.

II. A STUDY OF THE DYNAMICS OF TRIPLET EXCITONS IN MOLECULAR CRYSTALS

Phosphorescence spectra of pure crystalline naphthalene at room temperature and at 77˚ K are presented. The lifetime of the lowest triplet ³B_1u state of the crystal is determined from measurements of the time-dependence of the phosphorescence decay after termination of the excitation light. The fact that this lifetime is considerably shorter in the pure crystal at room temperature than in isotopic mixed crystals at 4.2˚ K is discussed, with special importance being attached to the mobility of triplet excitons in the pure crystal.

Excitation spectra of the delayed fluorescence and phosphorescence from crystalline naphthalene and anthracene are also presented. The equation governing the time- and spatial-dependence of the triplet exciton concentration in the crystal is discussed, along with several approximate equations obtained from the general equation under certain simplifying assumptions. The influence of triplet exciton diffusion on the observed excitation spectra and the possibility of using the latter to investigate the former is also considered. Calculations of the delayed fluorescence and phosphorescence excitation spectra of crystalline naphthalene are described.

A search for absorption of additional light quanta by triplet excitons in naphthalene and anthracene crystals failed to produce any evidence for the phenomenon. This apparent absence of triplet-triplet absorption in pure crystals is attributed to a low steady-state triplet concentration, due to processes like triplet-triplet annihilation, resulting in an absorption too weak to be detected with the apparatus used in the experiments. A comparison of triplet-triplet absorption by naphthalene in a glass at 77˚ K with that by naphthalene-h₈ in naphthalene-d₈ at 4.2˚ K is given. A broad absorption in the isotopic mixed crystal triplet-triplet spectrum has been tentatively interpreted in terms of coupling between the guest ³B_1u state and the conduction band and charge-transfer states of the host crystal.

III. AN INVESTIGATION OF DELAYED LIGHT EMISSION FROM Chlorella Pyrenoidosa

An apparatus capable of measuring emission lifetimes in the range 5 X 10^-9 sec to 6 X 10^-3 sec is described in detail. A cw argon ion laser beam, interrupted periodically by means of an electro-optic shutter, serves as the excitation source. Rapid sampling techniques coupled with signal averaging and digital data acquisition comprise the sensitive detection and readout portion of the apparatus. The capabilities of the equipment are adequately demonstrated by the results of a determination of the fluorescence lifetime of 5, 6, 11, 12-tetraphenyl-naphthacene in benzene solution at room temperature. Details of numerical methods used in the final data reduction are also described.

The results of preliminary measurements of delayed light emission from Chlorella Pyrenoidosa in the range 10^-3 sec to 1 sec are presented. Effects on the emission of an inhibitor and of variations in the excitation light intensity have been investigated. Kinetic analysis of the emission decay curves obtained under these various experimental conditions indicate that in the millisecond-to-second time interval the decay is adequately described by the sum of two first-order decay processes. The values of the time constants of these processes appear to be sensitive both to added inhibitor and to excitation light intensity.

Dynamics of the East Asian Summer Monsoon in Present and Future Climates

This thesis aims at enhancing our fundamental understanding of the East Asian summer monsoon (EASM), and mechanisms implicated in its climatology in present-day and warmer climates. We focus on the most prominent feature of the EASM, i.e., the so-called Meiyu-Baiu (MB), which is characterized by a well-defined, southwest to northeast elongated quasi-stationary rainfall band, spanning from eastern China to Japan and into the northwestern Pacific Ocean in June and July.

We begin with an observational study of the energetics of the MB front in present-day climate. Analyses of the moist static energy (MSE) budget of the MB front indicate that horizontal advection of moist enthalpy, primarily of dry enthalpy, sustains the front in a region of otherwise negative net energy input into the atmospheric column. A decomposition of the horizontal dry enthalpy advection into mean, transient, and stationary eddy fluxes identifies the longitudinal thermal gradient due to zonal asymmetries and the meridional stationary eddy velocity as the most influential factors determining the pattern of horizontal moist enthalpy advection. Numerical simulations in which the Tibetan Plateau (TP) is either retained or removed show that the TP influences the stationary enthalpy flux, and hence the MB front, primarily by changing the meridional stationary eddy velocity, with reinforced southerly wind on the northwestern flank of the north Pacific subtropical high (NPSH) over the MB region and northerly wind to its north. Changes in the longitudinal thermal gradient are mainly confined to the near downstream of the TP, with the resulting changes in zonal warm air advection having a lesser impact on the rainfall in the extended MB region.

Similar mechanisms are shown to be implicated in present climate simulations in the Couple Model Intercomparison Project - Phase 5 (CMIP5) models. We find that the spatial distribution of the EASM precipitation simulated by different models is highly correlated with the meridional stationary eddy velocity. The correlation becomes more robust when energy fluxes into the atmospheric column are considered, consistent with the observational analyses. The spread in the area-averaged rainfall amount can be partially explained by the spread in the simulated globally-averaged precipitation, with the rest primarily due to the lower-level meridional wind convergence. Clear relationships between precipitation and zonal and meridional eddy velocities are observed.

Finally, the response of the EASM to greenhouse gas forcing is investigated at different time scales in CMIP5 model simulations. The reduction of radiative cooling and the increase in continental surface temperature occur much more rapidly than changes in sea surface temperatures (SSTs). Without changes in SSTs, the rainfall in the monsoon region decreases (increases) over ocean (land) in most models. On longer time scales, as SSTs increase, rainfall changes are opposite. The total response to atmospheric CO^2 forcing and subsequent SST warming is a large (modest) increase in rainfall over ocean (land) in the EASM region. Dynamic changes, in spite of significant contributions from the thermodynamic component, play an important role in setting up the spatial pattern of precipitation changes. Rainfall anomalies over East China are a direct consequence of local land-sea contrast, while changes in the larger-scale oceanic rainfall band are closely associated with the displacement of the larger-scale NPSH. Numerical simulations show that topography and SST patterns play an important role in rainfall changes in the EASM region.

Changes in feeding biology of Nile tilapia, Oreochromis niloticus (L.), after invasion of water hyacinth, Eichhornia crassipes (Mart.) Solms, in Lake Victoria, Kenya

Oreochrimis niloticus (L.) was introduced to Lake victoria in the 1950s. It remained relatively uncommon in catches until 1965, when the numbers began to increase dramatically. It is now the third most important commercial fish species after the Nile perch, Lates niloticus (L.) and Rastrineobola argentea (Pellegrin). Oreochromis niloticus is considered a herbivore, feeding mostly on algae and plant material. The diet now appears to be more diversified , with insects, fish, algae and plant materials all being important food items. Fish smaller than 5 cm TL have a diverse diet but there is a decline in the importance of zooplankton, the preferred food item of small fish, as fish get larger. The shift in diet could be due to changes which have occurred in the lake. Water hyacinth, Eichhornia crassipes (Mart.) Solms, which harbours numerous insects in its root balls, now has extensively coverage over the lake. The native fish species which preyed on these insects (e.g. haplochromines) have largely been eliminated and O. niloticus could be filling niches previously occupied by these cichlids and non cichlid fishes. The change in diet could also be related to food availability and abundance where the fish is feeding on the most readily available food items.