Graduation Year

2005

Document Type

Thesis

Degree

M.S.

Degree Granting Department

Chemical Engineering

Major Professor

Venkat Bhethanabotla, Ph.D.

Committee Member

Scott Campbell, Ph.D.

Committee Member

Babu Joseph, Ph.D.

Keywords

TSM sensor, QCM, gas sensing

Abstract

Thickness shear mode (TSM) sensors, also known as quartz crystal micro-balances (QCM) are a class of acoustic wave sensors that have been used for gas/vapor sensing. Fast and sensitive chemical vapor sensing, specifically of hydrocarbon vapors is an important application for these vapor sensors. The TSM sensors typically used have a lower sensitivity compared with other acoustic wave sensors. This thesis describes the development of high sensitivity organic vapor sensors using thin polymer film coatings on TSM devices. Commercially available AT-quartz TSM devices were milled leaving a thin quartz membrane surrounded by a thicker outer ring. This resulted in an increased frequency and a consequent increase in sensitivity, as described by the Sauerbrey equation. The TSM sensors were then coated with thin sensing films of rubbery polymers. Isothermal experiments at room temperature were conducted. A fully instrumented and automated test bed consisting of a temperature-controlled organic vapor dilution system, a precision impedance analyzer, and computer based data acquisition was developed and used to evaluate the performance of the coated TSM devices. The TSM devices compared in this study were AT cut with fundamental resonant frequencies of 10, 20, and 96 MHz. The results of tests conducted are presented to demonstrate increase in sensitivity for higher fundamental frequency TSM devices. 96 MHz TSM resonators were found to be 8 to 27 times more sensitive than 10 MHz resonators. Sensitivity was limited by the difficulty in coating sensing layers and damping of the resonator. Additionally, each sensor was evaluated and compared in terms of detection limit and noise level. 96 MHz resonators had higher noise levels than 10 MHz or 20 MHz resonators; as a result, 96 MHz resonators did not show significant improvements in LOD. Also, response times for 96 MHz resonators were quicker than 10 MHz or 20 MHz resonators and response times generally decreased with analyte concentration. Several rubbery polymer films as well as copolymers were investigated to determine which sensing film would have the optimal performance in terms of response time, recovery, reproducibility, repeatability, frequency noise, and baseline drift.

The organic vapors studied were benzene, toluene, hexane, cyclohexane, heptane, dichloroethane, and chloroform at levels ranging from 0.2 to over 13.7 volume percentage in nitrogen gas. The Butterworth-VanDyke (BVD) equivalent circuit model was used to model both the perturbed and unperturbed TSM resonator. Monitoring the sensor response through the equivalent circuit model allowed for discriminating between the organic vapors. Vapor discrimination, in turn, depended upon the changes in the resistance parameter. Finally, the vapor liquid equilibrium at the polymer solvent interface was utilized to correct for perturbations, due to temperature changes, in the sensor response.

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