Steven Michael Thornberg

Investigation of microcantilever array with ordered nanoporous coatings for selective chemical detection

In this paper we demonstrate the potential for novel nanoporous framework materials (NFM) such as metal-organic frameworks (MOFs) 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. Detection of chemical weapons of mass destruction (CWMD), explosives, toxic industrial chemicals (TICs), and volatile organic compounds (VOCs) using micro-electro-mechanical-systems (MEMS) devices, such as microcantilevers and surface acoustic wave sensors, requires the use of recognition layers to impart selectivity. Traditional organic polymers are dense, impeding analyte uptake and slowing sensor response. The nanoporosity and ultrahigh surface areas of NFM enhance transport into and out of the NFM layer, improving response times, and their ordered structure enables structural tuning to impart selectivity. Here we describe experiments and modeling aimed at creating NFM layers tailored to the detection of water vapor, explosives, CWMD, and VOCs, and their integration with the surfaces of MEMS devices. Force field models show that a high degree of chemical selectivity is feasible. For example, using a suite of MOFs it should be possible to select for explosives vs. CWMD, VM vs. GA (nerve agents), and anthracene vs. naphthalene (VOCs). We will also demonstrate the integration of various NFM with the surfaces of MEMS devices and describe new synthetic methods developed to improve the quality of VFM coatings. Finally, MOF-coated MEMS devices show how temperature changes can be tuned to improve response times, selectivity, and sensitivity.

Isothermal mass flow measurements in microfabricated rectangular channels over a very wide Knudsen range

Measurement and modeling of gas flows in microelectromechanical systems (MEMS) scale channels are relevant to the fundamentals of rarefied gas dynamics (RGD) and the practical design of MEMS-based flow systems and micropumps. We describe techniques for building robust, leak-free, rectangular microchannels which are relevant to micro- and nanofluidic devices, while the channels themselves are useful for fundamental RGD studies. For the first time, we report the isothermal steady flow of helium (He) gas through these channels from the continuum to the free-molecular regime in the unprecedented Knudsen range of 0.03–1000. On the high end, our value is 20-fold larger than values previously reported by Ewart et al (2007 J. Fluid Mech. 584 337–56). We accomplished this through a dual-tank accumulation technique which enabled the monitoring of very low flow rates, below 10−14 kg s−1. The devices were prebaked under vacuum for 24 h at 100 °C in order to reduce outgassing and attain high Kn. We devised fabrication methods for controlled-depth micro-gap channels using silicon for both channel ceiling and floor, thereby allowing direct comparisons to models which utilize this simplifying assumption. We evaluated the results against a closed-form expression that accurately reproduces the continuum, slip, transition, and free-molecular regimes developed partly by using the direct simulation Monte Carlo method. The observed data were in good agreement with the expression. For Kn > ~100, we observed minor deviations between modeled and experimental flow values. Our fabrication processes and experimental data are useful to fundamental RGD studies and future MEMS microflow devices with respect to extremely low-flow measurements, model validation, and predicting optimal designs.

Surface Plasmon Sensing of Gas Phase Contaminants Using a Single-Ended Multiregion Optical Fiber

Fiber-optic gas phase surface plasmon resonance (SPR) detection of several contaminant gases of interest to state-of-health monitoring in high-consequence sealed systems has been demonstrated. These contaminant gases include H2, H2S, and moisture using a single-ended optical fiber mode. Data demonstrate that results can be obtained and sensitivity is adequate in a dosimetric mode that allows periodic monitoring of system atmospheres. Modeling studies were performed to direct the design of the sensor probe for optimized dimensions and to allow simultaneous monitoring of several constituents with a single sensor fiber. Testing of the system demonstrates the ability to detect 9 Pa partial pressures of H2 using this technique, <; 0.04 Pa partial pressures of H2S, and increases in H2O concentration from - 70°C frost point. In addition, a multiple sensor fiber has been demonstrated that allows a single fiber to measure H2, H2S, and H2O without changing the fiber or the analytical system.

Unified characterization of surfaces and gases in MEMS devices

Chemical and physical materials-aging processes can significantly degrade the long-term performance reliability of dormant microsystems. This degradation results from materials interactions with the evolving microenvironment by changing both bulk and interfacial properties (e.g., mechanical and fatigue strength, interfacial friction and stiction, electrical resistance). Eventually, device function is clearly threatened and as such, these aging processes are considered to have the potential for high (negative) consequences. Sandia National Laboratories is developing analytical characterization methodologies for identifying the chemical constituents of packaged microsystem environments, and test structures for proving these analytical techniques. To accomplish this, we are developing a MEMS test device containing structures expected to exhibit dormancy/analytical challenges, extending the range of detection for a series of analytical techniques, merging data from these separate techniques for greater information return, and developing methods for characterizing the internal atmosphere/gases. Surface analyses and data extraction have been demonstrated on surfaces of various geometries with different SAMS coatings, and gas analyses on devices with internal free volumes of 3 microliters have also been demonstrated.

Nanoliter MEMS package gas sampling to determine hermeticity

Maintaining the integrity of the internal atmosphere of a hermetic device is essential for long-term component reliability because it is within this environment that all internal materials age. As MEMS package sizes decrease with miniaturization, characterization of the internal atmosphere becomes increasingly difficult. Typical transistor metal cans (e.g., TO-5 type) and large MEMS devices have internal volumes of tenths of a milliliter. Last year, gas-sampling methods for smaller-sized MEMS packages were developed and successfully demonstrated on volumes as low as 3 microliters (package outside dimensions: ~1 x 2 x 5 mm). This year, we present gas sampling methods and results for a much smaller MEMS package having an internal volume of 30 nanoliters, two orders of magnitude lower than the previous small package. After entirely redesigning the previous sampling manifold, several of the 30 nanoliter MEMS were gas sampled successfully and results showed the intended internal gas atmosphere of nitrogen was sealed inside the package. The technique is a radical jump from previous methods because not only were these MEMS packages sampled, but also the gas from each package was analyzed dozens of times over the course of about 20 minutes. Additionally, alternate methods for gas analyses not using helium or fluorinert will be presented.

Method for creating gas standards form liquid HFE-7100 and FC-72.

HFE-7100 and FC-72 fluorinert are two fluids used during weapon component manufacturing. HFE-7100 is a solvent used in the cleaning of parts, and FC-72 is the blowing agent of a polymeric removable foam. The presence of either FC-72 or HFE-7100 gas in weapon components can provide valuable information as to the stability of the materials. Therefore, gas standards are needed so HFE-7100 and FC-72 gas concentrations can be accurately measured. There is no current established procedure for generating gas standards of either HFE-7100 or FC-72. This report outlines the development of a method to generate gas standards ranging in concentration from 0.1 ppm to 10% by volume. These standards were then run on a Jeol GC-Mate II mass spectrometer and analyzed to produce calibration curves. We present a manifold design that accurately generates gas standards of HFE-7100 and FC-72 and a procedure that allows the amount of each to be determined.

Performance characteristics of cryofocusing GC/MS system at BWXT Pantex Plant.

Ensuring the reliability of all components within a weapon system becomes increasingly important as the stockpile ages. One of the most noteworthy surveillance techniques designed to circumvent (or take place alongside) traditional D&I operations is to collect a sample of gas from within the internal atmosphere of a particular region in a weapon. While a wealth of information about the weapon may be encoded within the composition of its gas sample, our access to that information is only as good as the method used to analyze the sample. It has been shown that cryofocusing-GC/MS offers advantages in terms of sensitivity, ease of sample collection, and robustness of the equipment/hardware used. Attention is therefore focused on qualifying a cryo-GC/MS system for routine stockpile surveillance operations at Pantex. A series of tests were performed on this instrument to characterize the linearity and repeatability of its response using two different standard gas mixes (ozone precursor and TO-14) at various concentrations. This paper outlines the methods used and the results of these tests in order to establish a baseline by which to compare future cryo-GC/MS analyses. A summary of the results is shown.

Energy Efficient Catalytic Reaction and Production of Cumene

Alkylation reactions of benzene with propylene using zeolites were studied for their affinity for cumene production. The current process for the production of cumene involves heating corrosive acid catalysts, cooling, transporting, and distillation. This study focused on the reaction of products in a static one-pot vessel using non-corrosive zeolite catalysts, working towards a more efficient one-step process with a potentially large energy savings. A series of experiments were conducted to find the best reaction conditions yielding the highest production of cumene. The experiments looked at cumene formation amounts in two different reaction vessels that had different physical traits. Different zeolites, temperatures, mixing speeds, and amounts of reactants were also investigated to find their affects on the amount of cumene produced. Quantitative analysis of product mixture was performed by gas chromatography. Mass spectroscopy was also utilized to observe the gas phase components during the alkylation process.