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.

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.

Mortality, growth and growth rate variability of striped bass larvae in Chesapeake Subestuaries

In this report we develop age-length keys and derive age-frequency data. We estimate striped bass and white perch mortality and growth rates, based on the otolith-aging analysis. We also report on hatch-date frequencies of striped bass and white perch larvae, and we discuss environmental effects on recruitment potential.

Reference-growth rate – a simple and handy parameter summarizing the influence of environmental conditions

Abstract Environmental changes may have an impact on life conditions of the fish, e.g. food supply for the fish. The prevailing environmental conditions apply evenly to all age groups of one stock. Small fish have high growth rates, whereas large fish grow with low rates. But, it can be shown on the basis of the von Bertalanffy-growth model that it is sufficient to know only the growth rate of one single age group to compute the growth rates of all other age groups. The growth rate of a reference fish GRF (e.g. a fish with a body mass of 1 kg) was introduced as a reference growth describing the current food condition of all age groups of the stock. As an example a time series of the reference-growth rate of the northern cod stock (NAFO, 3K) was computed for the time span 1979 to 1999. For the northern cod stock it can be observed that environmental conditions caused growth rates below the long-term mean for seven years in a row. After a prolonged hunger period the fish stock collapsed in 1992 also by the impact of fisheries - and this was probably not a coincidence. Now, with the reference-growth rate GRF a simple and handy parameter was found to summarize the influence of the environmental conditions on growth and other derived models and therefore makes it easier to compute the influence of environmental changes within stock assessment. Zusammenfassung Veränderungen der Umwelt können Auswirkungen auf die Lebensbedingungen der Fische haben, z. B. auf das Nahrungsangebot der Fische. Die vorherrschenden Umgebungsbedingungen wirken gleichmäßig auf alle Altersgruppen eines Bestandes, wobei typischer Weise kleineFische hohe Wachstumsraten haben, während die großen Fische mit niedrigen Raten wachsen. Auf der Grundlage des von Bertalanffy-Wachstumsmodells kann gezeigt werden, dass es ausreicht, nur die Wachstumsrate von einer einzigen Altersgruppe zu kennen, um die Wachstumsraten von allen anderen Altersgruppen berechnen zu können. Die Wachstumsrate eines Referenz-Fisches (z.B. eines Fisches mit einer Körpermasse von 1 kg) wurde als Referenz-Wachstum GRF eingeführt, die den aktuellen Zustand des Nahrungsangebots füralle Altersgruppen des Bestandes beschreibt. Als Beispiel wurde einer Zeitreihe der Referenz-Wachstumsraten des nördlichen Kabeljaubestandes (NAFO, 3K) für die Zeitsraum 1979 bis 1999 berechnet. Für diesen Kabeljaubestand war zu beobachten, dass Umgebungsbedingungen für sieben Jahre in Folge Wachstumsraten unter dem langjährigen Mittelwert verursachten. Nach einer längeren Hungerperiode kollabierte dieser Fischbestand im Jahr 1992 auch durch den Einfluß der Fischerei - und dies war sicher kein Zufall. Jetzt, mit der Referenz-Wachstumsrate GRF, ist ein einfacher und handlicher Parameter gefunden, der es gestattet den Einfluss der Umweltbedingungen auf die Wachstumsbedingungen und andere davon abgeleitete Modelle zusammenzufassen. Dies macht es einfach, den Einfluss von Umweltveränderungen innerhalb der Bestandsabschätzungen zu berechnen.

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.

Aspects of the washout of salmonid eggs. 1. Observations on the physical characteristics of real and artificial eggs, their rate of fall in a water column and their pattern of settlement in an experimental channel

When salmonid redds are disrupted by spates, the displaced eggs will drift downstream. The mean distance of travel, the types of locations in which the eggs resettle and the depth of reburial of displaced eggs are not known. Investigation of these topics under field conditions presents considerable practical problems, though the use of artificial eggs might help to overcome some of them. Attempts to assess the similarities and/or differences in performance between real and artificial eggs are essential before artificial eggs can validly be used to simulate real eggs. The present report first compares the two types of egg in terms of their measurable physical characteristics (e.g. dimensions and density). The rate at which eggs fall in still water will relate to the rate at which they are likely to resettle in flowing water in the field. As the rate of fall will be influenced by a number of additional factors (e.g. shape and surface texture) which are not easily measured directly, the rates of fall of the two types of egg have been compared directly under controlled conditions. Finally, comparisons of the pattern of settlement of the two types of egg in flowing water in an experimental channel have been made. Although the work was primarily aimed at testing the value of artificial eggs as a simulation of real eggs, several side issues more directly concerned with the properties of real eggs and the likely distance of drift in natural streams have also been explored. This is the first of three reports made on this topic by the author in 1984.

基于傅里叶变换的光纤探头光谱特性校正方法的研究

针对光纤自身对光谱的非线性衰减的影响，提出了一种基于傅里叶变换的光谱校正方法。首先对是否经过光纤的两种情况下光电倍增管的输出电流进行傅里叶变换，得到光谱频域中的校正函数，然后通过傅里叶逆变换得到光谱域中的校正函数。为实现测试，建立一个光电检测系统，在可见光范围内进行测试。分别对是否带有光纤的两种情况下数据进行采集，使用该校正方法可以使光线的衰减得到较好的修正，误差小于1．54％。实验结果表明，该方法对特定的光纤传导系统的光谱非线性衰减有较好的校正效果。

The rate and mechanism of the partial oxidation of acetaldehyde by PPM concentrations of nitrogen dioxide

The thermal reaction between nitrogen dioxide and acetaldehyde in the gas phase was investigated at room temperature and atmospheric pressure. The initial rate of disappearance of nitrogen dioxide was 1.00 ± 0.03 order with respect to nitrogen dioxide and 1.00 ± 0.07 order with respect to acetaldehyde. An initial second order rate constant of (8.596 ± 0.189) x 10^-3 1.mole^-1 sec^-1 was obtained at 22.0 ± 0.1 °C and a total pressure of one atmosphere. The activation energy of the reaction was 12,900 cal/mole in the temperature range between 22°C and 122°C.

The products of the reaction were nitric oxide, carbon dioxide, methyl nitrite, nitromethane and a trace amount of trans-dimeric nitrosomethane. The addition of nitric oxide increased the rate of formation of nitromethane and decreased the rate of formation of methyl nitrite. There were no measurable surface effects due to the addition of glass wool or glass beads to the reactor.

Reactants and products were analyzed by gas chromatography. A mechanism was proposed incorporating the principal features of the reaction.

基于低速面阵CCD的正弦相位调制干涉测量

正弦相位调制(SPM)干涉测量技术用于表面形貌测量时, 需要帧速高于300 frame/s的图像传感器, 同时要求调制信号频率与图像传感器帧速成确定的整数倍关系。提出一种基于低速CCD(30 frame/s)的帧速可调的高速图像传感技术, 通过控制每帧像素总数提高CCD帧速, 研制出一种高帧速图像传感器, 帧速可达300～1600 frame/s, 且每帧大小连续可调。将该CCD传感器用于正弦相位调制干涉泰曼-格林干涉仪, 测量镀膜玻璃板表面形貌, 当CCD图像传感器的帧速与调制信号频率呈16, 8, 4

Repetition rate stabilization of the SBS Q-switched fiber laser by external injection

Repetition rate fluctuation is one of the main drawbacks of the low-threshold stimulated Brillouin scattering (SBS) Q-switched fiber laser. A method to stabilize the repetition rate is proposed in this paper by injecting a square-wave modulated light. It is measured experimentally that variance of the repetition rate can be improved from similar to 20% to similar to 1% of the period. It is also found that effectiveness of the method depends on modulation frequency and duty cycle of the injection. Its working mechanism is analyzed qualitatively. (C) 2009 Optical Society of America