Engineering topics

Baird, James K.

Publications and source records attributed to Baird, James K..

14 records

NASA NTRS2003

A Theory of the von Weimarn Rules Governing the Average Size of Crystals Precipitated from a Supersaturated Solution

More than 75 years ago, von Weimarn summarized his observations of the dependence of the average crystal size on the initial relative concentration supersaturation prevailing in a solution from which crystals were growing. Since then, his empirically derived rules have become part of the lore of crystal growth. The first of these rules asserts that the average crystal size measured at the end of a crystallization increases as the initial value of the relative supersaturation decreases. The second rule states that for a given crystallization time, the average crystal size passes through a maximum as a function of the initial relative supersaturation. Using a theory of nucleation and growth due to Buyevich and Mansurov, we calculate the average crystal size as a function of the initial relative supersaturation. We confirm the von Weimarn rules for the case where the nucleation rate is proportional to the third power or higher of the relative supersaturation.

Barlow, Douglas A.↗

NASA NTRS2001

Viscosity Relaxation in Molten HgZnTe

Rotating cup measurements of the viscosity of the pseudo-binary melt, HgZnTe have shown that the isothermal liquid with zinc mole fraction 0.16 requires tens of hours of equilibration time before a steady viscous state can be achieved. Over this relaxation period, the viscosity at 790 C increases by a factor of two, while the viscosity at 810 C increases by 40%. Noting that the Group VI elements tend to polymerize when molten, we suggest that the viscosity of the melt is enhanced by the slow formation of Te atom chains. To explain the build-up of linear Te n-mers, we propose a scheme, which contains formation reactions with second order kinetics that increase the molecular weight, and decomposition reactions with first order kinetics that inactivate the chains. The resulting rate equations can be solved for the time dependence of each molecular weight fraction. Using these molecular weight fractions, we calculate the time dependence of the average molecular weight. Using the standard semi-empirical relation between polymer average molecular weight and viscosity, we then calculate the viscosity relaxation curve. By curve fitting, we find that the data imply that the rate constant for n-mer formation is much smaller than the rate constant for n-mer deactivation, suggesting that Te atoms only weakly polymerize in molten HgZnTe. The steady state toward which the melt relaxes occurs as the rate of formation of an n-mer becomes exactly balanced by the sum of the rate for its deactivation and the rate for its polymerization to form an (n+1)-mer.

Su, Ching-Hua↗

NASA NTRS1998

The Effect of Solution Conditions on the Nucleation Kinetics of Tetragonal Lysozyme Crystals

An understanding of protein crystal nucleation rates and the effect of solution conditions upon them, is fundamental to the preparation of protein crystals of the desired size and shape for X-ray diffraction analysis. The ability to predict the effect of supersaturation, temperature, pH and precipitant concentration on the number and size of crystals formed is of great benefit in the pursuit of protein structure analysis. In this study we experimentally examine the effect of supersaturation, temperature, pH and sodium chloride concentration on the nucleation rate of tetragonal chicken egg white lysozyme crystals. In order to do this batch crystallization plates were prepared at given solution concentrations and incubated at three different temperatures over the period of one week. The number of crystals per well with their size and dimensions were recorded and correlated against solution conditions. Duplicate experiments indicate the reproducibility of the technique. Although it is well known that crystal numbers increase with increasing supersaturation, large changes in crystal number were also correlated against solution conditions of temperature, pH and salt concentration over the same supersaturation ranges. Analysis of these results enhance our understanding of the effect of solution conditions such as the dramatic effect that small changes in charge and ionic strength can have on the number of tetragonal lysozyme crystals that form and grow in solution.

Judge, Russell A.↗

NASA NTRS1993

Kinetics of diffusional droplet growth in a liquid/liquid two-phase system

This report contains experimental results for the interdiffusion coefficient of the system, succinonitrile plus water, at a number of compositions and temperatures in the single phase region of the phase diagram. The concentration and temperature dependence of the measured diffusion coefficient has been analyzed in terms of Landau - Ginzburg theory, which assumes that the Gibb free energy is an analytic function of its variables, and can be expanded in a Taylor series about any point in the phase diagram. At most points in the single phase region this is adequate. Near the consolute point (critical point of solution), however, the free energy is non-analytic, and the Landau - Ginzburg theory fails. The solution to this problem dictates that the Landau - Ginzburg form of the free energy be replaced by Widom scaling functions with irrational values for the scaling exponents. As our measurements of the diffusion coefficient near the critical point reflect this non-analytic character, we are preparing for publication in a refereed journal a separate analysis of some of the data contained herein as well as some additional measurements we have just completed. When published, reprints of this article will be furnished to NASA.

Baird, James K.↗

NASA NTRS1992

Series integration of the diaphragm cell transport equation when the diffusion coefficient is a function of concentration

An integral of the form, t = B0 + BL ln(Delta-c) + B1(Delta-c) + B2(Delta-c)-squared + ..., where t is the time and Delta-c is the concentration difference across the frit, is derived in the case of the diaphragm cell transport equation where the interdiffusion coefficient is a function of concentration. The coefficient, B0, is a constant of the integration, while the coefficients, BL, B1, B2,..., depend in general upon the constant, the compartment volumes, and the interdiffusion coefficient and various of its concentration derivatives evaluated at the mean concentration for the cell. Explicit formulas for BL, B1, B2,... are given.

Cain, Judith B.↗

NASA NTRS1992

Kinetics of diffusional droplet growth in a liquid/liquid two-phase system

In the case of the diaphragm cell transport equation where the interdiffusion coefficient is a function of concentration, we have derived an integral of the form, t = B(sub 0) + B(sub L)ln(delta(c)) + B(sub 1)(delta(c)) + B(sub 2)(delta(c))(exp 2) +... where t is the time and (delta(c)) is the concentration difference across the frit. The coefficient, B(sub 0), is a constant of integration, while the coefficient, B(sub L), B(sub 1), B(sub 2), ..., depend in general upon the cell constant, the compartment volumes, the interdiffusion coefficient, and various of its concentration derivatives evaluated at the mean concentration for the cell. Explicit formulae for B(sub L), B(sub 1), B(sub 2), ... are given.

Baird, James K.↗

NASA NTRS1991

Chemical waste disposal in space by plasma discharge

An inductively coupled plasma discharge apparatus operating at 13.56 MHz and with electrical power up to 2.5 kW was constructed. The efficiency of this device to destroy various gases expected to be carried aboard the Space Station was tested. By expressing the efficiency of the device in terms of G-value (the number of molecules decomposed per 100 eV of energy absorbed), the results are compared with known efficiencies of ionizing radiation to destroy these same gases. In the case of ammonia, it was found that in the inductively coupled device, the destruction efficiency, G(-NH3) varied from 6.0 to 32.0 molecules/100 eV, depending on conditions. It was also found that capacitatively coupled discharges were less efficient in destroying NH2 than the inductively coupled discharge. In the case NH2 destruction, it was found that the G(-NH3) was a qualitative guide to the efficiencies of plasmas. The plasma device was also used to destroy nitrous oxide and methane. It is shown how the G-value for the destruction of any gas can be computed theoretically from a knowledge of the electron velocity distribution, the various electron molecule scattering cross sections, and the rate constants for the reactions of secondary species.

Baird, James K.↗

NASA NTRS1990

The G value in plasma and radiation chemistry

The application of the G-value concept to plasma chemistry is considered. A general formula which expresses the G value for a general reaction in terms of experimentally controllable parameters is derived by applying simple gas-dynamic theory to a plasma reactor with straight walls. The formula expresses the G value as a function of the electrical power absorbed, the fraction of molecules transformed, and the flow rate of the gas entering the reactor. The formula was applied to the ammonia plasma radio-frequency discharge data of d'Agostino et al. (1981); the results showed that the G(-NH3) value lies in the range of 6.0-20 molecules/100 eV, depending on the conditions. This similarity of the G(-NH3) value with Peterson's (1974) range 2.7-10 found for the gas-phase radiolysis of ammonia, suggests that there might be a common reaction mechanism initiated by inelastic electron-molecule collisions.

Baird, James K.↗

NASA NTRS1988

The solubility of hen egg-white lysozyme

The equilibrium solubility of chicken egg-white lysozyme in the presence of crystalline solid state was determined as a function of NaCl concentration, pH, and temperature. The solubility curves obtained represent a region of the lysozyme phase diagram. This diagram makes it possible to determine the supersaturation of a given set of conditions or to achieve identical supersaturations by different combinations of parameters. The temperature dependence of the solubility permits the evaluation of Delta-H of crystallization. The data indicate a negative heat of crystallization for the tetragonal crystal form but a positive heat of crystallization for the high-temperature orthorhombic form.

Howard, Sandra B.↗

NASA NTRS1988

MCT crystal growth

Convection and segregation in directional solidification and crystal growth by the Bridgman-Stockbarger technique are traditionally treated by assuming axisymmetric thermal condition on the ampoule wall. It is, however, difficult to achieve such a condition in an experimental setup. Any deviation from an axisymmetric temperature field on the wall of a vertical ampoule represents a horizontal temperature gradient. The horizontal density gradient that results from thermal expansion in the melt under this condition must lead on earth to some buoyance-driven convection, no matter what the axial (vertical) temperature distribution that is imposed on the melt. The magnitude of such convective flows for conditions representative of the MSFC mercury-cadmium-telluride (MCT) Bridgman setup is studied.

Baird, James K.↗

NASA NTRS1987

Mass transport by diffusion

For the purpose of determining diffusion coefficients as required for electrodeposition studies and other applications, a diaphragm cell and an isothermal water bath were constructed. the calibration of the system is discussed. On the basis of three calibration runs on the diaphram cell, researchers concluded that the cell constant beta equals 0.12 cm -2 . Other calibration runs in progress should permit the cell constant to be determined with an accuracy of one percent.

Baird, James K.↗

NASA NTRS1987

Theory of atomic additivity in molecular hyperpolizabilities

Hyperpolarizability is a function of frequency. This is called dispersion. Because of the Kramers-Kronig relations, researchers expect that a material that is dispersing light is also absorbing it. Where there is both dispersion and absorption, the molecular polarizabilities are complex functions of the frequency. This led researchers to consider atomic additivity in both the real and imaginary parts of the ordinary and hyperpolarizabilities. This effort is desirable not only from a theoretical point of view, but also because of the existence of a large body of complex refractive index data, which may be used to test the additivity principle with the complex valued ordinary dipole polarizability.

Baird, James K.↗

NASA NTRS1987

Model for determining vapor equilibrium rates in the hanging drop method for protein crystal growth

An engineering analysis of the rate of evaporation of solvent in the hanging drop method of protein crystal growth is presented. Results are applied to 18 drop and well arrangements commonly encountered in the laboratory. The chemical nature of the salt, drop size and shape, drop concentration, well size, well concentration, and temperature are taken into account. The rate of evaporation increases with temperature, drop size, and the salt concentration difference between the drop and the well. The evaporation in this model possesses no unique half-life. Once the salt in the drop achieves 80 percent of its final concentration, further evaporation suffers from the law of diminishing returns.

Baird, James K.↗

NASA NTRS1987

Evaporation kinetics in the hanging drop method of protein crystal growth

An engineering analysis of the rate of evaporation of solvent in the hanging drop method of protein crystal growth is presented; these results are applied to 18 different drop and well arrangements commonly encountered in the laboratory, taking into account the chemical nature of the salt, the drop size and shape, the drop concentration, the well size, the well concentration, and the temperature. It is found that the rate of evaporation increases with temperature, drop size, and with the salt concentration difference between the drop and the well. The evaporation possesses no unique half-life. Once the salt in the drop achieves about 80 percent of its final concentration, further evaporation suffers from the law of diminishing returns.

Baird, James K.↗