William A. Goddard

Silicon nanowires as efficient thermoelectric materials

Thermoelectric materials interconvert thermal gradients and electric fields for power generation or for refrigeration. Thermoelectrics currently find only niche applications because of their limited efficiency, which is measured by the dimensionless parameter ZT—a function of the Seebeck coefficient or thermoelectric power, and of the electrical and thermal conductivities. Maximizing ZT is challenging because optimizing one physical parameter often adversely affects another. Several groups have achieved significant improvements in ZT through multi-component nanostructured thermoelectrics, such as Bi2Te3/Sb2Te3 thin-film superlattices, or embedded PbSeTe quantum dot superlattices. Here we report efficient thermoelectric performance from the single-component system of silicon nanowires for cross-sectional areas of 10u2009nmu2009×u200920u2009nm and 20u2009nmu2009×u200920u2009nm. By varying the nanowire size and impurity doping levels, ZT values representing an approximately 100-fold improvement over bulk Si are achieved over a broad temperature range, including ZTu2009≈u20091 at 200u2009K. Independent measurements of the Seebeck coefficient, the electrical conductivity and the thermal conductivity, combined with theory, indicate that the improved efficiency originates from phonon effects. These results are expected to apply to other classes of semiconductor nanomaterials.

Expanding the capabilities of the JPL electronic nose for an International Space Station technology demonstration

An array-based sensing system based on polymer/carbon composite conductometric sensors is under development at JPL for use as an environmental monitor in the International Space Station. Sulfur dioxide has been added to the analyte set for this phase of development. Using molecular modeling techniques, the interaction energy between SO2 and polymer functional groups has been calculated, and polymers selected as potential SO2 sensors. Experiment has validated the model and two selected polymers have been shown to be promising materials for SO2 detection.

Development of the Third Generation JPL Electronic Nose for International Space Station Technology Demonstration

The capabilities of the JPL Electronic Nose have been expanded to include characteristics required for a Technology Demonstration schedule on the International Space Station (ISS) in 2008-2009 [1,2]. Concurrently, to accommodate specific needs on ISS, the processes, tools and analyses which influence all aspects of development of the device have also been expanded. The Third Generation ENose developed for this program uses two types of sensor substrates, newly developed inorganic and organic sensor materials, redesigned electronics, onboard near real-time data analysis and power and data interfaces specifically for ISS. This paper will discuss the Third Generation ENose with a focus on detection of mercury in the parts-per-billion range.

LOWER COST METHODS FOR IMPROVED OIL RECOVERY (IOR) VIA SURFACTANT FLOODING

This report provides a summary of the work performed in this 3-year project sponsored by DOE. The overall objective of this project is to identify new, potentially more cost-effective surfactant formulations for improved oil recovery (IOR). The general approach is to use an integrated experimental and computational chemistry effort to improve our understanding of the link between surfactant structure and performance, and from this knowledge, develop improved IOR surfactant formulations. Accomplishments for the project include: (1) completion of a literature review to assemble current and new surfactant IOR ideas, (2) Development of new atomistic-level MD (molecular dynamic) modeling methodologies to calculate IFT (interfacial tension) rigorously from first principles, (3) exploration of less computationally intensive mesoscale methods to estimate IFT, Quantitative Structure Property Relationship (QSPR), and cohesive energy density (CED) calculations, (4) experiments to screen many surfactant structures for desirable low IFT and solid adsorption behavior, and (5) further experimental characterization of the more promising new candidate formulations (based on alkyl polyglycosides (APG) and alkyl propoxy sulfate surfactants). Important findings from this project include: (1) the IFT between two pure substances may be calculated quantitatively from fundamental principles using Molecular Dynamics, the same approach can provide qualitative results for ternary systemsmorexa0» containing a surfactant, (2) low concentrations of alkyl polyglycoside surfactants have potential for IOR (Improved Oil Recovery) applications from a technical standpoint (if formulated properly with a cosurfactant, they can create a low IFT at low concentration) and also are viable economically as they are available commercially, and (3) the alkylpropoxy sulfate surfactants have promising IFT performance also, plus these surfactants can have high optimal salinity and so may be attractive for use in higher salinity reservoirs. Alkylpropoxy sulfate surfactants are not yet available as large volume commercial products. The results presented herein can provide the needed industrial impetus for extending application (alkyl polyglycoside) or scaling up (alkylpropoxy sulfates) of these two promising surfactants for enhanced oil recovery. Furthermore, the advanced simulations tools presented here can be used to continue to uncover new types of surfactants with promising properties such as inherent low IFT and biodegradability.«xa0less

Cost Effective Surfactant Formulations for Improved Oil Recovery in Carbonate Reservoirs

This report summarizes work during the 30 month time period of this project. This was planned originally for 3-years duration, but due to its financial limitations, DOE halted funding after 2 years. The California Institute of Technology continued working on this project for an additional 6 months based on a no-cost extension granted by DOE. The objective of this project is to improve the performance of aqueous phase formulations that are designed to increase oil recovery from fractured, oil-wet carbonate reservoir rock. This process works by increasing the rate and extent of aqueous phase imbibition into the matrix blocks in the reservoir and thereby displacing crude oil normally not recovered in a conventional waterflood operation. The project had three major components: (1) developing methods for the rapid screening of surfactant formulations towards identifying candidates suitable for more detailed evaluation, (2) more fundamental studies to relate the chemical structure of acid components of an oil and surfactants in aqueous solution as relates to their tendency to wet a carbonate surface by oil or water, and (3) a more applied study where aqueous solutions of different commercial surfactants are examined for their ability to recover a West Texas crude oil from amorexa0» limestone core via an imbibition process. The first item, regarding rapid screening methods for suitable surfactants has been summarized as a Topical Report. One promising surfactant screening protocol is based on the ability of a surfactant solution to remove aged crude oil that coats a clear calcite crystal (Iceland Spar). Good surfactant candidate solutions remove the most oil the quickest from the surface of these chips, plus change the apparent contact angle of the remaining oil droplets on the surface that thereby indicate increased water-wetting. The other fast surfactant screening method is based on the flotation behavior of powdered calcite in water. In this test protocol, first the calcite power is pre-treated to make the surface oil-wet. The next step is to add the pre-treated powder to a test tube and add a candidate aqueous surfactant formulation; the greater the percentage of the calcite that now sinks to the bottom rather than floats, the more effective the surfactant is in changing the solids to become now preferentially water-wet. Results from the screening test generally are consistent with surfactant oil recovery performance reported in the literature. The second effort is a more fundamental study. It considers the effect of chemical structures of different naphthenic acids (NA) dissolved in decane as model oils that render calcite surfaces oil-wet to a different degree. NAs are common to crude oil and are at least partially responsible for the frequent observation that carbonate reservoirs are oil-wet. Because pure NA compounds are used, trends in wetting behavior can be related to NA molecular structure as measured by solid adsorption, contact angle and our novel, simple flotation test with calcite. Experiments with different surfactants and NA-treated calcite powder provide information about mechanisms responsible for sought after reversal to a water-wet state. Key findings include: (1) more hydrophobic NAs are more prone to induce oil-wetting, and (2) recovery of the model oil from limestone core was better with cationic surfactants, but one nonionic surfactant, Igepal CO-530, also had favorable results. This portion of the project included theoretical calculations to investigate key basic properties of several NAs such as their acidic strength and their relative water/oil solubility, and relate this to their chemical structure. The third category of this project focused on the recovery of a light crude oil from West Texas (McElroy Field) from a carbonate rock (limestone outcrop). For this effort, the first item was to establish a suite of surfactants that would be compatible with the McElroy Field brine. Those were examined further for their ability to recover oil by imbibition. Results demonstrate several types of promising candidates, and that within a given series of nonionic surfactants the oil recovery appears to be related to the HLB of each surfactant. For the McElroy brine and crude oil system, higher HLB (more water soluble) surfactants perform better than in earlier imbibition tests performed with the model oil and a fresh water or low salinity brine. We speculate that this difference mostly is because a more water soluble surfactant is required to be compatible with higher salinity of the McElroy brine (over 3 wt% salt).«xa0less

SCREENING METHODS FOR SELECTION OF SURFACTANT FORMULATIONS FOR IOR FROM FRACTURED CARBONATE RESERVOIRS

This topical report presents details of the laboratory work performed to complete Task 1 of this project; developing rapid screening methods to assess surfactant performance for IOR (Improved Oil Recovery) from fractured carbonate reservoirs. The desired outcome is to identify surfactant formulations that increase the rate and amount of aqueous phase imbibition into oil-rich, oil-wet carbonate reservoir rock. Changing the wettability from oil-wet to water-wet is one key to enhancing this water-phase imbibition process that in turn recovers additional oil from the matrix portion of a carbonate reservoir. The common laboratory test to evaluate candidate surfactant formulations is to measure directly the aqueous imbibition rate and oil recovery from small outcrop or reservoir cores, but this procedure typically requires several weeks. Two methods are presented here for the rapid screening of candidate surfactant formulations for their potential IOR performance in carbonate reservoirs. One promising surfactant screening protocol is based on the ability of a surfactant solution to remove aged crude oil that coats a clear calcite crystal (Iceland Spar). Good surfactant candidate solutions remove the most oil the quickest from the chips, plus change the apparent contact angle of the remaining oil droplets on the surface that thereby indicate increasedmorexa0» water-wetting. The other fast surfactant screening method is based on the flotation behavior of powdered calcite in water. In this test protocol, first the calcite power is pre-treated to make the surface oil-wet. The next step is to add the pre-treated powder to a test tube and add a candidate aqueous surfactant formulation; the greater the percentage of the calcite that now sinks to the bottom rather than floats, the more effective the surfactant is in changing the solids to become now preferentially water-wet. Results from the screening test generally are consistent with surfactant performance reported in the literature.«xa0less