Publications

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We will describe how novel nanoporous framework materials (NFM) such as metal-organic frameworks (MOFs) can be interfaced with common mechanical sensors, such as surface acoustic wave (SAW), microcantilever array, and quartz crystal microbalance (QCM) devices, and subsequently be used to provide selectivity and sensitivity to a broad range of analytes including explosives, nerve agents, and volatile organic compounds (VOCs). NFM are highly ordered, crystalline materials with considerable synthetic flexibility resulting from the presence of both organic and inorganic components within their structure. Chemical detection using micro-electro-mechanical-systems (MEMS) devices (i.e. SAWs, microcantilevers) requires the use of recognition layers to impart selectivity. Unlike traditional organic polymers, which are dense, the nanoporosity and ultrahigh surface areas of NFM allow for greater analyte uptake and enhance transport into and out of the sensing layer. This enhancement over traditional coatings leads to improved response times and greater sensitivity, while their ordered structure allows chemical tuning to impart selectivity. We describe here experiments and modeling aimed at creating NFM layers tailored to the detection of water vapor, explosives, CWMD, and volatile organic compound (VOCs), and their integration with the surfaces of MEMS devices. Molecular simulation shows that a high degree of chemical selectivity is feasible. For example, a suite of MOFs can select for strongly interacting organics (explosives, CWMD) vs. lighter volatile organics at trace concentrations. At higher gas pressures, the CWMD are deselected in favor of the volatile organics. We will also demonstrate the integration of various NFM on the surface of microcantiliver arrays, QCM crystals, and SAW devices, and describe new synthetic methods developed to improve the quality of NFM coatings. Finally, MOF-coated MEMS devices show how temperature changes can be tuned to improve response times, selectivity, and sensitivity.

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Fiber-optic sensors for sensing electrical current are attractive due to their inherent immunity to electromagnetic interference. Several groups have shown the use of Faraday rotation in magneto-optical materials as a function of current-induced magnetic field. In this work, fiber-optic sensors based on different mechanisms such as magnetic-fielddependent polarization coherence and power scattering effects in magneto-optical materials are demonstrated. These novel sensor configurations can have advantages in that they exhibit power-independent or polarization-independent operation which can ultimately lead to fewer components and relaxed light source requirements compared to fiber-optic current sensor systems based on Faraday rotation.

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This thesis presents the theory, design, fabrication and testing of the microvalves and columns necessary in a pressure- and temperature-programmed micro gas chromatograph ({micro}GC). Two microcolumn designs are investigated: a bonded Si-glass column having a rectangular cross section and a vapor-deposited silicon oxynitride (Sion) column having a roughly circular cross section. Both microcolumns contain integrated heaters and sensors for rapid, controlled heating. The 3.2 cm x 3.2 cm, 3 m-long silicon-glass column, coated with a non-polar polydimethylsiloxane (PDMS) stationary phase, separates 30 volatile organic compounds (VOCs) in less than 6 min. This is the most efficient micromachined column reported to date, producing greater than 4000 plates/m. The 2.7 mm x 1.4 mm Sion column eliminates the glass sealing plate and silicon substrate using deposited dielectrics and is the lowest power and fastest GC column reported to date; it requires only 11 mW to raise the column temperature by 100 C and has a response time of 11s and natural temperature ramp rate of 580 C/min. A 1 m-long PDMS-coated Sion microcolumn separates 10 VOCs in 52s. A system-based design approach was used for both columns.

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The gas-phase {mu}ChemLab{trademark} developed by Sandia can detect volatile organics and semi-volatiles organics via gas phase sampling . The goal of this three year Laboratory Directed Research and Development (LDRD) project was to adapt the components and concepts used by the {mu}ChemLab{trademark} system towards the analysis of water-borne chemicals of current concern. In essence, interfacing the gas-phase {mu}ChemLab{trademark} with water to bring the significant prior investment of Sandia and the advantages of microfabrication and portable analysis to a whole new world of important analytes. These include both chemical weapons agents and their hydrolysis products and disinfection by-products such as Trihalomethanes (THMs) and haloacetic acids (HAAs). THMs and HAAs are currently regulated by EPA due to health issues, yet water utilities do not have rapid on-site methods of detection that would allow them to adjust their processes quickly; protecting consumers, meeting water quality standards, and obeying regulations more easily and with greater confidence. This report documents the results, unique hardware and devices, and methods designed during the project toward the goal stated above. It also presents and discusses the portable field system to measure THMs developed in the course of this project.

The adsorption and desorption behavior of a planar microfabricated preconcentrator (PC) has been modeled and simulated using the computational fluid dynamics (CFD) package CFDRC-ACE+trade. By comparison with the results of a designed experiment, model parameters were determined. Assuming a first-order reaction for the adsorption of a light hydrocarbon chemical analyte onto the PC adsorbent and a unity-value sticking coefficient, a rate constant of 36,500 s{sup -1} was obtained. This compares favorably with the value of 25,300 s{sup -1} obtained by application of the Modified-Wheeler equation. The modeled rate constant depends on the concentration of adsorbent sites, estimated to be 6.94 ldr 10{sup -8} kmol/m{sup 2} for the Carboxen 1000 adsorbent used. Using the integral method, desorption was found to be first order with an Arrhenius temperature dependence and an activation energy of 30.1 kj/mol. Validation of this model is reported herein, including the use of Aris-Taylor dispersion to predict the influence of fluidics surrounding the PC. A maximum in desorption peak area with flow rate, predicted from a quadratic fit to the results of the designed experiment, was not observed in the 2-D simulation. Either approximations in the simulated model or the nonphysical nature of the quadratic fit are responsible. Despite the apparent simplicity of the model, the simulation is internally self consistent and capable of predicting performance of new device designs. To apply the method to other analytes and other adsorbent materials, only a limited number of comparisons to experiment are required to obtain the necessary rate constants.

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Networked systems of low-cost, small, integrable chemical sensors will enable monitoring of Nonproliferation and Materials Control targets and chemical weapons threats. Sandia-designed prototype chemical sensor systems are undergoing extended field testing supported by DOE and other government agencies. A required surety component will be verification of microanalytical system performance, which can be achieved by providing a programmable source of chemical signature(s) for autonomous calibration of analytical systems. In addition, such a controlled chemical source could be used to dispense microaliquots of derivatization reagents, extending the analysis capability of chemical sensors to a wider range of targets. We have developed a microfabricated system for controlled release of selected compounds (calibrants) into the analytical stream of microsensor systems. To minimize pumping and valve requirements of microfluidic systems, and to avoid degradation issues associated with storage of dilute solutions, we have utilized thermally labile organic salts as solid-phase reservoir materials. Reproducible deposition of tetrapropyl ammonium hydroxide onto arrays of microfabricated heating elements can provide a pair of calibration marker compounds (one fast and one slow-eluting compound) for GC analyses. The use of this microaliquot gas source array for hydrogen generation is currently under further development. The goal of the latter effort will be to provide a source of high-pressure, low viscosity GC carrier gas for Sandia's next-generation microfabricated gas-phase chemical analysis systems.

This paper surveys the needs associated with environmental monitoring and long-term environmental stewardship. Emerging sensor technologies are reviewed to identify compatible technologies for various environmental monitoring applications. The contaminants that are considered in this report are grouped into the following categories: (1) metals, (2) radioisotopes, (3) volatile organic compounds, and (4) biological contaminants. United States regulatory drivers are evaluated for different applications (e.g., drinking water, storm water, pretreatment, and air emissions), and sensor requirements are derived from these regulatory metrics. Sensor capabilities are then summarized according to contaminant type, and the applicability of the different sensors to various environmental monitoring applications is discussed.

This report surveys the needs associated with environmental monitoring and long-term environmental stewardship. Emerging sensor technologies are reviewed to identify compatible technologies for various environmental monitoring applications. The contaminants that are considered in this report are grouped into the following categories: (1) metals, (2) radioisotopes, (3) volatile organic compounds, and (4) biological contaminants. Regulatory drivers are evaluated for different applications (e.g., drinking water, storm water, pretreatment, and air emissions), and sensor requirements are derived from these regulatory metrics. Sensor capabilities are then summarized according to contaminant type, and the applicability of the different sensors to various environmental monitoring applications is discussed.