Edward T. Zellers

Multiple-stage microfabricated preconcentrator-focuser for micro gas chromatography system

The design, fabrication, and characterization of a multiple-stage Si microfabricated preconcentrator-focuser (/spl mu/PCF) for a micro gas chromatography (/spl mu/GC) system that can provide real-time quantification and identification of complex organic vapor mixtures are presented. The /spl mu/PCF consists of a Si microheater loaded with Carbopack B, Carbopack X, and Carboxen 1000 carbon adsorbent granules, and a Si micromachined cover plate. Deep reactive ion etching is utilized to produce mechanically robust fluidic interconnection adapters hermetically sealed to fused silica capillary tubing for connection to the other components in the /spl mu/GC. This three-stage device is designed to capture compounds spanning up to 4 orders of magnitude in volatility. The dead volume, thermal mass, heating efficiency, and pressure drop of the three-stage /spl mu/PCF are improved significantly over its single-stage /spl mu/PCF predecessor. We demonstrate the successful capture, desorption, and high-resolution chromatographic separation of a mixture of 30 common organic vapors using our three-stage /spl mu/PCF in a conventional GC system. The peak width at half height is <2.05 s for all compounds after elution from the GC column.

Microfabricated preconcentrator-focuser for a microscale gas chromatograph

The design, fabrication, and testing of a preconcentrator-focuser (PCF), consisting of a thick micromachined Si heater packed with a small quantity of a granular adsorbent material are described. The PCF is developed to capture and concentrate vapors for subsequent focused thermal desorption and analysis in a micro gas chromatograph. The microheater contains an array of high-aspect-ratio, etched-Si heating elements, 520 /spl mu/m (h)/spl times/50 /spl mu/m (w)/spl times/3000 /spl mu/m (l), bounded by an annulus of Si and thermally isolated from the remaining substrate by an air gap. This structure is sandwiched between Pyrex glass plates with inlet/outlet ports that accept capillary tubes for sample flow and is sealed by anodic bonding (bottom) and rapidly annealed glass/metal/Si solder bonding (top). The large microheater surface area allows for high adsorption capacity and efficient, uniform thermal desorption of vapors captured on the adsorbent within the structure. The adsorbent consists of roughly spherical granules, /spl sim/200 /spl mu/m in diameter, of a high-surface-area, graphitized carbon. Key design considerations, fabrication technologies, and results of performance tests are presented with an emphasis on the thermal desorption characteristics of several representative volatile organic compounds as a function of volumetric flow rates and heating rates. Preconcentration factors as high as 5600 and desorbed peak widths as narrow as 0.8 s are achieved from 0.25-L samples of benzene at modest heating rates. The effects of operating variables on sensitivity, chromatographic resolution, and detection limits are assessed. Testing of this PCF with a micromachined separation column and integrated sensor array is discussed briefly.

Microfabricated Gas Chromatograph for the Selective Determination of Trichloroethylene Vapor at Sub-Parts-Per-Billion Concentrations in Complex Mixtures

A complete field-deployable microfabricated gas chromatograph (μGC) is described, and its adaptation to the analysis of low- and subparts-per-billion (ppb) concentrations of trichloroethylene (TCE) vapors in complex mixtures is demonstrated through laboratory testing. The specific application being addressed concerns the problem of indoor air contamination by TCE vapor intrusion. The μGC prototype employs a microfabricated focuser, dual microfabricated separation columns, and a microsensor array. These are interfaced to a nonmicrofabricated front-end pretrap and high-volume sampler module to reduce analysis time and limits of detection (LOD). Selective preconcentration and focusing are coupled with rapid chromatographic separation and multisensor detection for the determination of TCE in the presence of up to 45 interferences. Autonomous operation is possible via a laptop computer. Preconcentration factors as high as 500 000 are achieved. Sensitivities are constant over the range of captured TCE masses tested (i.e., 9-390 ng), and TCE is measured in a test atmosphere at 120 parts-per-trillion (ppt), with a projected LOD of 40 ppt (4.2 ng captured, 20 L sample) and a maximum sampling + analytical cycle time of 36 min. Short- and medium-term (1 month) variations in retention time, absolute responses, and response patterns are within acceptable limits.

Vapor recognition with an integrated array of polymer-coated flexural plate wave sensors

Abstract Preliminary testing of a prototype instrument employing an integrated array of six polymer-coated flexural plate wave (FPW) sensors and an adsorbent preconcentrator is described. Responses to thermally desorbed samples of individual organic solvent vapors and binary and ternary vapor mixtures are linear with concentration, and mixture responses are equivalent to the sums of the responses of the component vapors, which co-elute from the preconcentrator in most cases. Limits of detection as low as 0.3 ppm are achieved from a 60-s (34 cm 3 ) air sample and peak widths at half-maximum range from 1 to 4 s. Tests at different flow rates suggest that the kinetics of vapor sorption in the sensor coating films may limit responses at higher flow rates, however, low data acquisition rates may also be contributory. Assessments of array performance using independent test data and Monte Carlo simulations with pattern recognition indicate that individual vapors and certain binary and ternary mixtures can be recognized/discriminated with very low error. More complex mixtures, and those containing homologous vapors, are problematic. This is the first report demonstrating multi-vapor analysis with an integrated FPW sensor array.

An Integrated Micro-Analytical System for Complex Vapor Mixtures

A micro gas chromatograph (muGC) capable of quantitatively analyzing the components of complex vapor mixtures at trace concentrations is described. The muGC features a micro- preconcentrator/focuser (muPCF), dual-column pressure- and temperature-programmed separation module, and an integrated array of nanoparticle-coated chemiresistors. The latest design modifications and performance data are presented. Highlights include a 4-min separation of a 30-component mixture with a 3-m DRIE Si/glass microcolumn, a 14-sec separation of an 11-component mixture on a 25-cm microcolumn, a complete multi-vapor analysis from a hybrid microsystem that combines analytical, rf- wireless, and microcontroller modules, and a rapid analysis driven by a 4-stage peristaltic micropump.

Microfabricated thermal modulator for comprehensive two-dimensional micro gas chromatography: design, thermal modeling, and preliminary testing

In comprehensive two-dimensional gas chromatography (GC x GC), a modulator is placed at the juncture between two separation columns to focus and re-inject eluting mixture components, thereby enhancing the resolution and the selectivity of analytes. As part of an effort to develop a microGC x microGC prototype, in this report we present the design, fabrication, thermal operation, and initial testing of a two-stage microscale thermal modulator (microTM). The microTM contains two sequential serpentine Pyrex-on-Si microchannels (stages) that cryogenically trap analytes eluting from the first-dimension column and thermally inject them into the second-dimension column in a rapid, programmable manner. For each modulation cycle (typically 5 s for cooling with refrigeration work of 200 J and 100 ms for heating at 10 W), the microTM is kept approximately at -50 degrees C by a solid-state thermoelectric cooling unit placed within a few tens of micrometres of the device, and heated to 250 degrees C at 2800 degrees C s(-1) by integrated resistive microheaters and then cooled back to -50 degrees C at 250 degrees C s(-1). Thermal crosstalk between the two stages is less than 9%. A lumped heat transfer model is used to analyze the device design with respect to the rates of heating and cooling, power dissipation, and inter-stage thermal crosstalk as a function of Pyrex-membrane thickness, air-gap depth, and stage separation distance. Experimental results are in agreement with trends predicted by the model. Preliminary tests using a conventional capillary column interfaced to the microTM demonstrate the capability for enhanced sensitivity and resolution as well as the modulation of a mixture of alkanes.

Limits of Recognition for Binary and Ternary Vapor Mixtures Determined with Multitransducer Arrays

The discrimination of simple vapor mixtures from their components with polymer-coated multitransducer (MT) arrays as a function of the absolute and relative concentrations of those components is explored. The data set consists of calibrated responses to 11 organic vapors from arrays of 5 or 8 microsensors culled from a group of 5 cantilever, 5 capacitor, and 5 calorimeter transducers coated with 1 of 5 different sorptive-polymer films. Monte Carlo methods are applied to simulate error-enhanced composite responses to all possible binary and ternary mixtures of the 11 vapors, and principal component regression models are established for estimating expected rates of recognition as a function of mixture composition. The limit of recognition (LOR), defined as the maximum recognizable mixture composition range, is used as the metric of performance. With the optimal 8-sensor MT array, 19 binary and 3 ternary mixtures could be identified (i.e., discriminated from their components) with <5% error. The binary-mixture LORs are shown to decrease with increases in the baseline noise levels and random sensitivity variations of the sensors, as well as the similarity of the vapors. Importantly, most of the binary LOR contours are significantly asymmetric with respect to composition, and none of the mixtures could be recognized with <5% error at component relative concentration ratios exceeding 20:1. Discrimination of ternary mixtures from their components and binary subcomponent mixtures is possible only if the relative concentration ratio between any two of the components is <5:1. In comparing binary LORs for the best five-sensor single-transducer (ST) array to those of the best five-sensor MT array, the latter were larger in nearly all cases. The implications of these results are considered in the context of using such arrays as detectors in microanalytical systems with upstream chromatographic modules.

A Micropump-Driven High-Speed MEMS Gas Chromatography System

We report (1) the integration of the first functioning MEMS gas chromatography system ( muGC) featuring a micropump, a micro-column, and a micro-chemiresistor sensor array; and (2) experimental demonstration of the state-of-the-art multi-vapor gas separation and detection. In particular, we report the best GC analysis data from the first micropump-driven muGC system to date: the separation and detection of 11 volatile organic compounds (VOC)s within only 78 seconds while consuming only 15.1 mW of power within a small volume of 0.5 cc. We also report the use of temperature programming (TP) of the separation column for fast analysis, which shortened the analysis time from 78 seconds to 24 seconds while maintaining gas analysis resolution.

MODELING THE TEMPERATURE DEPENDENCE OF N-METHYLPYRROLIDONE PERMEATION THROUGH BUTYL- AND NATURAL-RUBBER GLOVES

This paper describes the temperature dependence of N-methylpyrrolidone (NMP) permeation through gloves used in microelectronics fabrication facilities. One type of butyl-rubber glove (North B161), two types of natural-rubber gloves (Edmont Puretek and Ansell Pacific White), and a natural rubber/nitrile/neoprene-blend glove (Pioneer Trionic) were tested at four temperatures from 25-50 degrees C using the ASTM F739-85 permeation test method. The butyl-rubber glove showed no breakthrough after four hours of exposure at any temperature. The variations with temperature of measured breakthrough times (BT) and steady-state permeation rates (SSPR) for the other gloves were described well by Arrhenius relationships, with BT values decreasing by factors of 7-10 and SSPR values increasing by factors of 4-6 over the temperature range studied. Extrapolation to 70 and 93 degrees C, the temperatures at which degreasing is often performed, yielded BT values of < 2 min and < 0.5 min, respectively, in all cases. With the exception of the butyl-rubber glove, following an initial exposure at 25 degrees C and air drying overnight, low levels of NMP vapor were detected off-gassing from the inner surfaces of the gloves. Experimental results were then compared to those expected from several permeation models. Estimates of the equilibrium solvent solubility, S, were calculated using a model based on three-dimensional solubility parameters. Estimates of the solvent diffusion coefficient, D, were obtained from correlations with either the solvent kinematic viscosity or the product of the Flory interaction parameter, chi, and the solvent molar volume. Combining these values of D and S in Fickian diffusion equations gave modeled BT estimates that were within 23% of experimental values over the temperature range examined. Modeled SSPR values were within 50% (typically within 25%) of experimental values. Another model based on a generalized Arrhenius relationship also provided useful but generally less accurate estimates of the changes in BT and SSPR values with temperature.

Comprehensive two-dimensional gas chromatographic separations with a microfabricated thermal modulator

Rapid, comprehensive two-dimensional gas chromatographic (GC × GC) separations by use of a microfabricated midpoint thermal modulator (μTM) are demonstrated, and the effects of various μTM design and operating parameters on performance are characterized. The two-stage μTM chip consists of two interconnected spiral etched-Si microchannels (4.2 and 2.8 cm long) with a cross section of 250 × 140 μm(2), an anodically bonded Pyrex cap, and a cross-linked wall coating of poly(dimethylsiloxane) (PDMS). Integrated heaters provide rapid, sequential heating of each μTM stage, while a proximate, underlying thermoelectric cooler provides continual cooling. The first-dimension column used for GC × GC separations was a 6 m long, 250 μm i.d. capillary with a PDMS stationary phase, and the second-dimension column was a 0.5 m long, 100 μm i.d. capillary with a poly(ethylene glycol) phase. Using sets of five to seven volatile test compounds (boiling point ≤174 °C), the effects of the minimum (T(min)) and maximum (T(max)) modulation temperature, stage heating lag/offset (O(s)), modulation period (P(M)), and volumetric flow rate (F) on the quality of the separations were evaluated with respect to several performance metrics. Best results were obtained with a T(min) = -20 °C, T(max) = 210 °C, O(s) = 600 ms, P(M) = 6 s, and F = 0.9 mL/min. Replicate modulated peak areas and retention times were reproducible to <5%. A structured nine-component GC × GC chromatogram was produced, and a 21 component separation was achieved in <3 min. The potential for creating portable μGC × μGC systems is discussed.