Chris D. Muzny

Clay platelet dispersion in a polymer matrix

A dispersed clay/polymer nanocomposite was prepared by joining, via a cationic exchange reaction, surfactant monomers to clay platelets and subsequently polymerizing them with acrylamide. Dispersion was made possible by preparing a clay surfactant precursor solution, with the surfactant in sufficient excess to form clay-micelle complexes that resist platelet aggregation. This homogeneous nanoscale dispersion of platelets was verified using dynamic light scattering.

New Group-Contribution Approach to Thermochemical Properties of Organic Compounds: Hydrocarbons and Oxygen-Containing Compounds

A new group-contribution approach involving systematic corrections for 1,4-non-bonded carbon-carbon and carbon-oxygen interactions has been proposed. Limits of the applicability of the method, associated with the highly branched structures, were established. Experimental data for enthalpies of formation in the liquid phase, enthalpies of vaporization, and enthalpies of formation in the gas phase for alkanes, alkenes, alkynes, alkylbenzenes, alkanols, ethers, ketones and aldehydes, carboxylic acids, esters, and carbonates were collected and critically evaluated through dynamic data evaluation as implemented in the NIST ThermoData Engine. An automatic procedure for molecular structure “decomposition” was developed, and algorithms for the assessment of expanded uncertainties for the predicted property values were implemented. The combination of these software tools allows for ongoing improvements of the group-contribution parameter set as new experimental data become available. Fifty-two group-contribution p...

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 3. Binary mixtures.

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported in this journal. The present paper describes the first application of this concept to the evaluation of thermophysical properties for ternary chemical systems. The method involves construction of Redlich-Kister type equations for individual properties (excess volume, thermal conductivity, viscosity, surface tension, and excess enthalpy) and activity coefficient models for phase equilibrium properties (vapor-liquid and liquid-liquid equilibrium). Constructed ternary models are based on those for the three pure component and three binary subsystems evaluated on demand through the TDE software algorithms. All models are described in detail, and extensions to the class structure of the program are provided. Reliable evaluation of properties for the binary subsystems is essential for successful property evaluations for ternary systems, and algorithms are described to aid appropriate parameter selection and fitting for the implemented activity coefficient models (NRTL, Wilson, Van Laar, Redlich-Kister, and UNIQUAC). Two activity coefficient models based on group contributions (original UNIFAC and NIST-KT-UNIFAC) are also implemented. Novel features of the user interface are shown, and directions for future enhancements are outlined.

ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept. 4. Chemical Reactions

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. This paper describes the first application of this concept to the evaluation of thermodynamic properties for chemical reactions. Reaction properties evaluated are the enthalpies, entropies, Gibbs energies, and thermodynamic equilibrium constants. Details of key considerations in the critical evaluation of enthalpies of formation and of standard entropies for organic compounds are discussed in relation to their application in the calculation of reaction properties. Extensions to the class structure of the program are described that allow close linkage between the derived reaction properties and the underlying pure-component properties. Derivation of pure-component enthalpies of formation and of standard entropies through the use of directly measured reaction properties (enthalpies of reaction and equilibrium constants) is described. Directions for future enhancements are outlined.

ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept. 5. Experiment Planning and Product Design§

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. In the present paper, we describe development of an algorithmic approach to assist experiment planning through assessment of the existing body of knowledge, including availability of experimental thermophysical property data, variable ranges studied, associated uncertainties, state of prediction methods, and parameters for deployment of prediction methods and how these parameters can be obtained using targeted measurements, etc., and, indeed, how the intended measurement may address the underlying scientific or engineering problem under consideration. A second new feature described here is the application of the software capabilities for aid in the design of chemical products through identification of chemical systems possessing desired values of thermophysical properties within defined ranges of tolerance. The algorithms and their software implementation to achieve this are described. Finally, implementation of a new data validation and weighting system is described for vapor-liquid equilibrium (VLE) data, and directions for future enhancements are outlined.

A SANS Study of Organoclay Dispersions

Small-angle neutron scattering (SANS) is used to investigate the dispersion in toluene of various forms of the complex, Cloisite C15A. Cloisite is a commercially important exchanged clay prepared from montmorillonite and the cation di-tallow ammonium. Points discussed include estimates of the extent to which the complex is dispersed, the amount of organic clay platelet surface layer coverage, and possible network formation of the complex in the solvent. From power-law plots of the scattered neutron intensity versus the wave vector, it is estimated that C15A is well dispersed into clusters which consist of a stack of between three and seven di-tallow-coated montmorillonite platelets. The removal of excess di-tallow from the surface layer reduces the number of platelets in the cluster. Substitution of dimethydioctodecyl ammonium for the di-tallow molecule promotes network formation. It is demonstrated that SANS is a powerful tool for examining these complicated organic/inorganic systems.

ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept. 9. Extensible Thermodynamic Constraints for Pure Compounds and New Model Developments

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported in this journal. The present article describes the background and implementation for new additions in latest release of TDE. Advances are in the areas of program architecture and quality improvement for automatic property evaluations, particularly for pure compounds. It is shown that selection of appropriate program architecture supports improvement of the quality of the on-demand property evaluations through application of a readily extensible collection of constraints. The basis and implementation for other enhancements to TDE are described briefly. Other enhancements include the following: (1) implementation of model-validity enforcement for specific equations that can provide unphysical results if unconstrained, (2) newly refined group-contribution parameters for estimation of enthalpies of formation for pure compounds containing carbon, hydrogen, and oxygen, (3) implementation of an enhanced group-contribution method (NIST-Modified UNIFAC) in TDE for improved estimation of phase-equilibrium properties for binary mixtures, (4) tools for mutual validation of ideal-gas properties derived through statistical calculations and those derived independently through combination of experimental thermodynamic results, (5) improvements in program reliability and function that stem directly from the recent redesign of the TRC-SOURCE Data Archival System for experimental property values, and (6) implementation of the Peng-Robinson equation of state for binary mixtures, which allows for critical evaluation of mixtures involving supercritical components. Planned future developments are summarized.

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 8. Properties of material streams and solvent design.

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported in this journal. The present paper describes the first application of this concept to the evaluation of thermophysical properties for material streams involving any number of chemical components with assessment of uncertainties. The method involves construction of Redlich-Kister type equations for individual properties (excess volume, thermal conductivity, viscosity, surface tension, and excess enthalpy) and activity-coefficient models for phase equilibrium properties (vapor-liquid equilibrium). Multicomponent models are based on those for the pure-components and all binary subsystems evaluated on demand through the TDE software algorithms. Models are described in detail, and extensions to the class structure of the program are provided. Novel program features, such as ready identification of key measurements for subsystems that can reduce the combined uncertainty for a particular stream property, are described. In addition, new product-design features are described for selection of solvents for optimized crystal dissolution, separation of binary crystal mixtures, and solute extraction from a single-component solvent. Planned future developments are summarized.

ThermoData Engine (TDE): software implementation of the dynamic data evaluation concept. 6. Dynamic web-based data dissemination through the NIST Web Thermo Tables.

ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. In the present paper, we describe the development of a World Wide Web-based interface to TDE evaluations of pure compound properties, including critical properties, phase boundary equilibria (vapor pressures, sublimation pressures, and crystal-liquid boundary pressures), densities, energetic properties, and transport properties. This includes development of a system for caching evaluation results to maintain high availability and an advanced window-in-window interface that leverages modern Web-browser technologies. Challenges associated with bringing the principal advantages of the TDE technology to the Web are described, as are compromises to maintain general access and speed of interaction while remaining true to the tenets of dynamic data evaluation. Future extensions of the interface and associated Web-services are outlined.

Shear-induced restructuring of concentrated colloidal silica gels

The viscometric properties and structure of concentrated sheared colloidal gels, formed at a pH = 8 from a commercial aqueous sol of 7 nm diameter silica particles, were investigated. As the system gels under a constant shear rate, the viscosity first increases, then peaks when the shear stress reaches a shear-rate-independent threshold value of about 350 Pa, and finally decreases asymptotically to approximately one tenth the peak value. This low-viscosity state can apparently be held indefinitely by maintaining the shear, but the system gels once the shear is removed. The structural origins of this viscometric behaviour were studied using in situ small-angle neutron scattering (SANS). An abrupt change in the character of the SANS intensity was observed at the time corresponding to the peak in the viscosity. Samples of the gelling system were extracted and diluted at various times after gel initiation. Effective hydrodynamic diameters of these extractants were estimated by dynamic light scattering, and their Guinier diameters were estimated by SANS when appropriate. We conclude that the drop in viscosity corresponds to a structural densification of growing clusters of the colloidal particles, and that this transformation occurs once the critical stress is reached.