Steven M. Thornberg

Ultrasensitive Humidity Detection Using Metal–Organic Framework-Coated Microsensors

The use of metal-organic framework (MOF) thin films to detect water vapor across a wide concentration range is demonstrated using MOF-functionalized quartz surface acoustic wave (SAW) sensors. A range of 3-14,800 ppmv was obtained with thin films of the MOF Cu(3)(benzenetricarboxylate)(2) (Cu-BTC) deposited by an automated layer-by-layer method. Devices coated by a manual technique demonstrated sensitivity from 0.28 to 14,800 ppmv, the limit of our test system. This exceeds the sensitivity of many commercially available sensors. Cu-BTC layers were covalently bonded directly to the silicon oxide surface, allowing devices to be heated beyond 100 °C to desorb water adsorbed in the pores without decomposition, thereby regenerating the sensors. Sensor response as a function of coating thickness was evaluated, showing that the SAW sensor response is bounded by maximum and minimum layer thicknesses. Computer simulation of H(2)O uptake shows a multistep adsorption isotherm defined by initial adsorption at open Cu-sites, followed by pore-filling and finally full saturation. Modeling and experimental results are consistent. Calculated uptake values suggest an efficient adsorption of H(2)O by Cu-BTC. These results provide the first convincing evidence that MOF functionalization of compact sensing technologies such as SAW devices and microcantilevers can compete with state-of-the art devices.

SEDIDAT: a BASIC program for the collection and staXtistical analysis of partice settling velocity data

Abstract SEDIDAT is a series of compiled IBM-BASIC (version 2.0) programs that direct the collection, statistical calculation, and graphic presentation of particle settling velocity and equivalent spherical diameter for samples analyzed using the settling tube technique. The programs follow a menu-driven format that is understood easily by students and scientists with little previous computer experience. Settling velocity is measured directly (cm,sec) and also converted into Chi units. Equivalent spherical diameter (reported in Phi units) is calculated using a modified Gibbs equation for different particle densities. Input parameters, such as water temperature, settling distance, particle density, run time, and Phi;Chi interval are changed easily at operator discretion. Optional output to a dot-matrix printer includes a summary of moment and graphic statistical parameters, a tabulation of individual and cumulative weight percents, a listing of major distribution modes, and cumulative and histogram plots of a raw time, settling velocity. Chi and Phi data.

Luminescence Instrument for the Acquisition of Low-Temperature Fluorescence and Phosphorescence Spectra

An inexpensive, simple (but highly automated) instrument for acquiring high-resolution fluorescence and phosphorescence spectra of polycyclic aromatic hydrocarbons (PAHs) is described. Fluorescence and phosphorescence signals are processed by gated integration and photon counting, respectively. The instrument can be used to acquire excitation as well as emission spectra in both the frequency and time domain. In addition, a method for measuring single and double exponential phosphorescence decay times is presented. Decay times ranging from 0.3 ms to 300 ms were measured for several naphthalene derivatives, with a precision of ∼10%. The primary advantages of this instrument are high sensitivity, high selectivity, wide linear dynamic ranges, and a versatile range of applications.

Selective stress-based microcantilever sensors for enhanced surveillance.

Assessment of component aging and degradation in weapon systems remains a considerable challenge for the Integrated Stockpile Evaluation program. Analysis of weapon atmospheres can provide degradation signatures and indicate the presence of corrosive vapors. However, a critical need exists for compatible in-situ sensors to detect moisture and other gases over stockpile lifetimes. This inhibits development of both “self-aware weapons” and fully instrumented weapon test platforms that could provide in-situ data to validate high-fidelity models for gases within weapons. We developed platforms for on-demand weapon atmosphere surveillance based on static microcantilevers (SMC) and surface accoustic wave (SAW) devices coated with nanoporous metal organic frameworks (MOFs) to provide selectivity. SMC detect analytes via adsorbate-induced stress and are up to 100X more sensitive than resonant

Precision Moisture Generation and Measurement

In many industrial processes, gaseous moisture is undesirable as it can lead to metal corrosion, polymer degradation, and other materials aging processes. However, generating and measuring precise moisture concentrations is challenging due to the need to cover a broad concentration range (parts-per-billion to percent) and the affinity of moisture to a wide range surfaces and materials. This document will discuss the techniques employed by the Mass Spectrometry Laboratory of the Materials Reliability Department at Sandia National Laboratories to generate and measure known gaseous moisture concentrations. This document highlights the use of a chilled mirror and primary standard humidity generator for the characterization of aluminum oxide moisture sensors. The data presented shows an excellent correlation in frost point measured between the two instruments, and thus provides an accurate and reliable platform for characterizing moisture sensors and performing other moisture related experiments.

Surface plasmon sensing of gas phase contaminants using 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 H{sub 2}, H{sub 2}S, 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 70mTorr partial pressures of H{sub 2} using this technique and <280 {micro}Torr partial pressures of H{sub 2}S. In addition, a multiple sensor fiber has been demonstrated that allows a single fiber to measure H{sub 2}, H{sub 2}S, and H{sub 2}O without changing the fiber or the analytical system.