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Advances in analytical chemistry

Implementation of computer programs based on multivariate statistical algorithms makes possible obtaining reliable information from long data vectors that contain large amounts of extraneous information, for example, noise and/or analytes that we do not wish to control. Three examples are described. Each of these applications requires the use of techniques characteristic of modern analytical chemistry. The first example, using a quantitative or analytical model, describes the determination of the acid dissociation constant for 2,2'-pyridyl thiophene using archived data. The second example describes an investigation to determine the active biocidal species of iodine in aqueous solutions. The third example is taken from a research program directed toward advanced fiber-optic chemical sensors. The second and third examples require heuristic or empirical models.

Arendale, W. F.↗

Analytical evaluation of a surface integral expressing the coupling between interior and exterior volumes in a FE-IE approach

Recently an approach which combines the finite element technique and an integral equation to determine the fields scattered by inhomogeneous bodies of complicated shape has been proposed. Basically, a mathematical surface which encloses the scatterers is introduced, thus dividing the space into an interior and an exterior volume, in which the finite element technique and an integral equation for EM scattering, respectively, are applied. The integral equation is set up for the tangential components of the fields at the surface, while the interior volume the unknowns are the total fields. Continuity of the tangential fields at the boundary, as required by Maxwell's equations, is imposed, thus coupling the two methods to obtain a consistent solution. The coupling term is expressed by a surface integral formed by the dot product of a FE basis function and an IE testing function, or viceversa. By choosing the boundary to be a surface of revolution and by making a convenient selection of IE basis (testing) functions, it is possible to evaluate the integrals analytically on surfaces such as curved triangles, curved quadrilaterals and curved pentagons. We will illustrate the salient steps involved in setting up and carrying out these integrals and discuss what class of basis (testing) functions and analytic surfaces of revolution they are applicable to. Analytic calculations offer the advantage of better accuracy than purely numerical ones, and, when combined with them, often shed light on issues of numerical convergence and limiting values. Furthermore, they may reduce computation time and storage requirements.

Zuffada, C.↗

Reliability-based structural optimization: A proposed analytical-experimental study

An analytical and experimental study for assessing the potential of reliability-based structural optimization is proposed and described. In the study, competing designs obtained by deterministic and reliability-based optimization are compared. The experimental portion of the study is practical because the structure selected is a modular, actively and passively controlled truss that consists of many identical members, and because the competing designs are compared in terms of their dynamic performance and are not destroyed if failure occurs. The analytical portion of this study is illustrated on a 10-bar truss example. In the illustrative example, it is shown that reliability-based optimization can yield a design that is superior to an alternative design obtained by deterministic optimization. These analytical results provide motivation for the proposed study, which is underway.

Stroud, W. Jefferson↗

Analytical control test plan and microbiological methods for the water recovery test

Qualitative and quantitative laboratory results are important to the decision-making process. In some cases, they may represent the only basis for deciding between two or more given options or processes. Therefore, it is essential that handling of laboratory samples and analytical operations employed are performed at a deliberate level of conscientious effort. Reporting erroneous results can lead to faulty interpretations and result in misinformed decisions. This document provides analytical control specifications which will govern future test procedures related to all Water Recovery Test (WRT) Phase 3 activities to be conducted at the National Aeronautics and Space Administration/Marshall Space Flight Center (NASA/MSFC). This document addresses the process which will be used to verify analytical data generated throughout the test period, and to identify responsibilities of key personnel and participating laboratories, the chains of communication to be followed, and ensure that approved methodology and procedures are used during WRT activities. This document does not outline specifics, but provides a minimum guideline by which sampling protocols, analysis methodologies, test site operations, and laboratory operations should be developed.

Traweek, M. S.↗

Validation of the SINDA/FLUINT code using several analytical solutions

The Systems Improved Numerical Differencing Analyzer and Fluid Integrator (SINDA/FLUINT) code has often been used to determine the transient and steady-state response of various thermal and fluid flow networks. While this code is an often used design and analysis tool, the validation of this program has been limited to a few simple studies. For the current study, the SINDA/FLUINT code was compared to four different analytical solutions. The thermal analyzer portion of the code (conduction and radiative heat transfer, SINDA portion) was first compared to two separate solutions. The first comparison examined a semi-infinite slab with a periodic surface temperature boundary condition. Next, a small, uniform temperature object (lumped capacitance) was allowed to radiate to a fixed temperature sink. The fluid portion of the code (FLUINT) was also compared to two different analytical solutions. The first study examined a tank filling process by an ideal gas in which there is both control volume work and heat transfer. The final comparison considered the flow in a pipe joining two infinite reservoirs of pressure. The results of all these studies showed that for the situations examined here, the SINDA/FLUINT code was able to match the results of the analytical solutions.

Keller, John R.↗

Experimental and analytical characterization of triaxially braided textile composites

There were two components, experimental and analytical, to this investigation of triaxially braided textile composite materials. The experimental portion of the study centered on measuring the materials' longitudinal and transverse tensile moduli, Poisson's ratio, and strengths. The identification of the damage mechanisms exhibited by these materials was also a prime objective of the experimental investigation. The analytical portion of the investigation utilized the Textile Composites Analysis (TECA) model to predict modulus and strength. The analytical and experimental results were compared to assess the effectiveness of the analysis. The figures contained in this paper reflect the presentation made at the conference. They may be divided into four sections: a definition of the material system tested; followed by a series of figures summarizing the experimental results (these figures contain results of a Moire interferometry study of the strain distribution in the material, examples and descriptions of the types of damage encountered in these materials, and a summary of the measured properties); a description of the TECA model follows the experimental results (this includes a series of predicted results and a comparison with measured values); and finally, a brief summary completes the paper.

Masters, John E.↗

Analytical model for the density distribution in the Io plasma torus

An analytical model is developed for the diffusive equilibrium plasma density distribution in the Io plasma torus. The model has been employed successfully to follow the ray path of plasma waves in the multi-ion Jovian magnetosphere; it would also be valuable for other studies of the Io torus that require a smooth and continuous description of the plasma density and its gradients. Validity of the analytical treatment requires that the temperature of thermal electrons be much lower than the ion temperature and that superthermal electrons be much less abundant than the thermal electrons; these two conditions are satisfied in the warm outer region of the Io torus from L = 6 to L = 10. The analytical solutions agree well with exact numerical calculations for the most dense portion of the Io torus within 30 deg of the equator.

Mei, YI↗

An innovative approach to the development of a portable unit for analytical flame characterization in a microgravity environment

The availability of manned laboratory facilities in space offers wonderful opportunities and challenges in microgravity combustion science and technology. In turn, the fundamentals of microgravity combustion science can be studied via spectroscopic characterization of free radicals generated in flames. The laser-induced fluorescence (LIF) technique is a noninvasive method of considerable utility in combustion physics and chemistry suitable for monitoring not only specific species and their kinetics, but it is also important for imaging of flames. This makes LIF one of the most important tools for microgravity combustion science. Flame characterization under microgravity conditions using LIF is expected to be more informative than other methods aimed at searching for effects like pumping phenomenon that can be modeled via ground level experiments. A primary goal of our work consisted in working out an innovative approach to devising an LIF-based analytical unit suitable for in-space flame characterization. It was decided to follow two approaches in tandem: (1) use the existing laboratory (non-portable) equipment and determine the optimal set of parameters for flames that can be used as analytical criteria for flame characterization under microgravity conditions; and (2) use state-of-the-art developments in laser technology and concentrate some effort in devising a layout for the portable analytical equipment. This paper presents an up-to-date summary of the results of our experiments aimed at the creation of the portable device for combustion studies in a microgravity environment, which is based on a portable UV tunable solid-state laser for excitation of free radicals normally present in flames in detectable amounts. A systematic approach has allowed us to make a convenient choice of species under investigation, as well as the proper tunable laser system, and also enabled us to carry out LIF experiments on free radicals using a solid-state laser tunable in the UV.

Dubinskiy, Mark A.↗

Analytic MHD Theory for Earth's Bow Shock at Low Mach Numbers

A previous MHD theory for the density jump at the Earth's bow shock, which assumed the Alfven M(A) and sonic M(s) Mach numbers are both much greater than 1, is reanalyzed and generalized. It is shown that the MHD jump equation can be analytically solved much more directly using perturbation theory, with the ordering determined by M(A) and M(s), and that the first-order perturbation solution is identical to the solution found in the earlier theory. The second-order perturbation solution is calculated, whereas the earlier approach cannot be used to obtain it. The second-order terms generally are important over most of the range of M(A) and M(s) in the solar wind when the angle theta between the normal to the bow shock and magnetic field is not close to 0 deg or 180 deg (the solutions are symmetric about 90 deg). This new perturbation solution is generally accurate under most solar wind conditions at 1 AU, with the exception of low Mach numbers when theta is close to 90 deg. In this exceptional case the new solution does not improve on the first-order solutions obtained earlier, and the predicted density ratio can vary by 10-20% from the exact numerical MHD solutions. For theta approx. = 90 deg another perturbation solution is derived that predicts the density ratio much more accurately. This second solution is typically accurate for quasi-perpendicular conditions. Taken together, these two analytical solutions are generally accurate for the Earth's bow shock, except in the rare circumstance that M(A) is less than or = 2. MHD and gasdynamic simulations have produced empirical models in which the shock's standoff distance a(s) is linearly related to the density jump ratio X at the subsolar point. Using an empirical relationship between a(s) and X obtained from MHD simulations, a(s) values predicted using the MHD solutions for X are compared with the predictions of phenomenological models commonly used for modeling observational data, and with the predictions of a modified phenomenological model proposed recently. The similarities and differences between these results are illustrated using plots of X and a(s) predicted for the Earth's bow shock. The plots show that the new analytic solutions agree very well with the exact numerical MHD solutions and that these MHD solutions should replace the corresponding phenomenological relations in comparisons with data. Furthermore, significant differences exist between the standoff distances predicted at low M(A) using the MHD models versus those predicted by the new modified phenomenological model. These differences should be amenable to observational testing.

Grabbe, Crockett L.↗

Analytical Studies of Boundary Layer Generated Aircraft Interior Noise

An analysis is made of the "interior noise" produced by high, subsonic turbulent flow over a thin elastic plate partitioned into "panels" by straight edges transverse to the mean flow direction. This configuration models a section of an aircraft fuselage that may be regarded as locally flat. The analytical problem can be solved in closed form to represent the acoustic radiation in terms of prescribed turbulent boundary layer pressure fluctuations. Two cases are considered: (i) the production of sound at an isolated panel edge (i.e., in the approximation in which the correlation between sound and vibrations generated at neighboring edges is neglected), and (ii) the sound generated by a periodic arrangement of identical panels. The latter problem is amenable to exact analytical treatment provided the panel edge conditions are the same for all panels. Detailed predictions of the interior noise depend on a knowledge of the turbulent boundary layer wall pressure spectrum, and are given here in terms of an empirical spectrum proposed by Laganelli and Wolfe. It is expected that these analytical representations of the sound generated by simplified models of fluid-structure interactions can used to validate more general numerical schemes.

Howe, M. S.↗

Analytical and Experimental Determination of the Coupled Natural Frequencies and Mode Shapes of a Dynamic Model of a Single-Rotor Helicopter

A combined analytical and experimental determination is made of the coupled natural frequencies and mode shapes in the longitudinal plane of symmetry for a dynamic model of a single-rotor helicopter. The analytical phase is worked out on the basis of a seven-degree-of-freedom system combining elastic deflections of the rotor blades, rotor shaft, pylon, and fuselage. The calculated coupled frequencies are first compared with calculated uncoupled frequencies to show the general effects of coupling and then with measured coupled frequencies to determine the extent to which the coupled frequencies can be calculated. The coupled mode shapes are also calculated and were observed visually with stroboscopic lights during the tests. A comparison of the coupled and uncoupled natural frequencies shows that significant differences exist between these frequencies for some of the modes. Good agreement is obtained between the measured and calculated values for the coupled natural frequencies and mode shapes. The results show that the coupled natural frequencies and mode shapes can be determined by the analytical procedure presented herein with sufficient accuracy if the mass and stiffness distributions of the various components of the helicopter are known.

Silveira, Milton A.↗

Analytical and Computational Aspects of Collaborative Optimization

Bilevel problem formulations have received considerable attention as an approach to multidisciplinary optimization in engineering. We examine the analytical and computational properties of one such approach, collaborative optimization. The resulting system-level optimization problems suffer from inherent computational difficulties due to the bilevel nature of the method. Most notably, it is impossible to characterize and hence identify solutions of the system-level problems because the standard first-order conditions for solutions of constrained optimization problems do not hold. The analytical features of the system-level problem make it difficult to apply conventional nonlinear programming algorithms. Simple examples illustrate the analysis and the algorithmic consequences for optimization methods. We conclude with additional observations on the practical implications of the analytical and computational properties of collaborative optimization.

Alexandrov, Natalia M.↗

A Comparison of Analytical and Experimental Data for a Magnetic Actuator

Theoretical and experimental force-displacement and force-current data are compared for two configurations of a simple horseshoe, or bipolar, magnetic actuator. One configuration utilizes permanent magnet wafers to provide a bias flux and the other configuration has no source of bias flux. The theoretical data are obtained from two analytical models of each configuration. One is an ideal analytical model which is developed under the following assumptions: (1) zero fringing and leakage flux, (2) zero actuator coil mmf loss, and (3) infinite permeability of the actuator core and suspended element flux return path. The other analytical model, called the extended model, is developed by adding loss and leakage factors to the ideal model. The values of the loss and leakage factors are calculated from experimental data. The experimental data are obtained from a magnetic actuator test fixture, which is described in detail. Results indicate that the ideal models for both configurations do not match the experimental data very well. However, except for the range around zero force, the extended models produce a good match. The best match is produced by the extended model of the configuration with permanent magnet flux bias.

Groom, Nelson J.↗

Notch Sensitivity of Woven Ceramic Matrix Composites Under Tensile Loading: An Experimental, Analytical, and Finite Element Study

The stress concentrations associated with circular notches and subjected to uniform tensile loading in woven ceramic matrix composites (CMCs) have been investigated for high-efficient turbine engine applications. The CMC's were composed of Nicalon silicon carbide woven fabric in SiNC matrix manufactured through polymer impregnation process (PIP). Several combinations of hole diameter/plate width ratios and ply orientations were considered in this study. In the first part, the stress concentrations were calculated measuring strain distributions surrounding the hole using strain gages at different locations of the specimens during the initial portion of the stress-strain curve before any microdamage developed. The stress concentration was also calculated analytically using Lekhnitskii's solution for orthotropic plates. A finite-width correction factor for anisotropic and orthotropic composite plate was considered. The stress distributions surrounding the circular hole of a CMC's plate were further studied using finite element analysis. Both solid and shell elements were considered. The experimental results were compared with both the analytical and finite element solutions. Extensive optical and scanning electron microscopic examinations were carried out for identifying the fracture behavior and failure mechanisms of both the notched and notched specimens. The stress concentration factors (SCF) determined by analytical method overpredicted the experimental results. But the numerical solution underpredicted the experimental SCF. Stress concentration factors are shown to increase with enlarged hole size and the effects of ply orientations on stress concentration factors are observed to be negligible. In all the cases, the crack initiated at the notch edge and propagated along the width towards the edge of the specimens.

Haque, A.↗

Analytical and Experimental Study of Near-Threshold Interactions Between Crack Closure Mechanisms

The results of an analytical closure model that considers contributions and interactions between plasticity-, roughness-, and oxide-induced crack closure mechanisms are presented and compared with experimental data. The analytical model is shown to provide a good description of the combined influences of crack roughness, oxide debris, and plasticity in the near-threshold regime. Furthermore, analytical results indicate that closure mechanisms interact in a non-linear manner such that the total amount of closure is not the sum of closure contributions for each mechanism.

Newman, John A.↗

Experimental Evaluation of Analytical Models for the Inertias and Natural Frequencies of Fuel Sloshing in Circular Cylindrical Tanks

A correlation is presented of experimental measurement and analytical prediction of free, planar oscillations of a tank of mercury hung on a pendulum. Measured frequencies are presented for the slosh mode and the pendulum-tank mode, and time-history wave forms are included for qualitative comparisons. The sloshing is represented analytically by a single pendulum or a spring-bob, and the size and location of their inertias are determined by matching forces and moments on the tank surface with linearized hydrodynamic theory for inviscid fluids. It is concluded that such analytical models are identical for small displacements in the present application (as they are in simpler applications) and that they provide excellent simulation of the stiffness and in ertia terms for fuel sloshing.

Warner, Robert W.↗

Molecular modeling of polymer composite-analyte interactions in electronic nose sensors

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL electronic nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereoisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings with no hydrogens. The Dreiding 2.21 force field is used for the polymer, solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4-vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic and organic compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites. c2003 Elsevier Science B.V. All rights reserved.

NASA Center JPL↗

Nine-analyte detection using an array-based biosensor

A fluorescence-based multianalyte immunosensor has been developed for simultaneous analysis of multiple samples. While the standard 6 x 6 format of the array sensor has been used to analyze six samples for six different analytes, this same format has the potential to allow a single sample to be tested for 36 different agents. The method described herein demonstrates proof of principle that the number of analytes detectable using a single array can be increased simply by using complementary mixtures of capture and tracer antibodies. Mixtures were optimized to allow detection of closely related analytes without significant cross-reactivity. Following this facile modification of patterning and assay procedures, the following nine targets could be detected in a single 3 x 3 array: Staphylococcal enterotoxin B, ricin, cholera toxin, Bacillus anthracis Sterne, Bacillus globigii, Francisella tularensis LVS, Yersiniapestis F1 antigen, MS2 coliphage, and Salmonella typhimurium. This work maximizes the efficiency and utility of the described array technology, increasing only reagent usage and cost; production and fabrication costs are not affected.

NASA Discipline Life Sciences Technologies↗