Characterization of Plasticizer-Polymer Coatings for the Detection of Benzene in Water Using Sh- Saw Devices Jude Coompson Marquette University
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Marquette University e-Publications@Marquette Master's Theses (2009 -) Dissertations, Theses, and Professional Projects Characterization of Plasticizer-Polymer Coatings for the Detection of Benzene in Water Using Sh- Saw Devices Jude Coompson Marquette University Recommended Citation Coompson, Jude, "Characterization of Plasticizer-Polymer Coatings for the Detection of Benzene in Water Using Sh-Saw Devices" (2015). Master's Theses (2009 -). Paper 315. http://epublications.marquette.edu/theses_open/315 CHARACTERIZATION OF PLASTICIZER-POLYMER COATINGS FOR THE DETECTION OF BENZENE IN WATER USING SH-SAW DEVICES by Jude K Coompson, B.S. A Thesis submitted to the Faculty of the Graduate School, Marquette University, in Partial Fulfillment of the Requirements for the Degree of Master of Science Milwaukee, WI CHARACTERIZATION OF PLASTICIZER-POLYMER COATINGS FOR THE DETECTION OF BENZENE IN WATER USING SH-SAW DEVICES ABSTRACT Jude K. Coompson, B.S. Marquette University, 2014 Benzene is a constituent component of crude oil that has been classified as a carcinogen by the EPA with a maximum contamination level (MCL) of 5ppb in drinking water. However, of the aromatic compounds, benzene has one of the lowest polymer-water partition coefficients using commercially available polymers as sensor coatings, resulting in poor limits of detection. This work investigates new coating materials based on polymer/plasticizer mixtures coated onto a shear horizontal surface acoustic wave (SH-SAW) sensor to detect benzene in water. There are many polymers which are unavailable for use as a sensing polymer due to their glassy nature. The use of plasticizers allows the polymer properties to be modified to give a more sensitive polymer by reducing the glass transition temperature, Tg, and increasing the free volume creating a more rubbery polymer which will absorb benzene. Three polymers, polystyrene (PS), poly (ethyl acrylate) and poly (methyl acrylate) were chosen to be plasticized with dioctyl phthalate (DOP). Polystyrene, which also possesses benzene rings, was chosen as its glass transition temperature is 100°C making it glassy. PEA was chosen because it has previously been used as a sensing polymer for benzene and has a Tg of -21°C. PMA was chosen because it has a Tg of 9°C and has previously been shown to have a low sensitivity to benzene. Dioctyl phthalate was chosen as the plasticizer because it possesses a benzene ring and had previously been used as a plasticizer in industry and research for polystyrene and acrylate polymers. The plasticizer-polymer mixtures are spin coated on a lithium tantalate (LiTaO 3) SH-SAW dual delay-line device at various thicknesses. Each coating was exposed to multiple concentrations of benzene and frequency shifts were measured. Plasticization led to increased sensitivity for all polymers to benzene. i ACKNOLEDGEMENTS JUDE K. COOMPSON, B.S. I would like to express my gratitude to my advisor Dr. Fabien Josse for the time and effort he has invested in me and my research. I would also like to thank Dr. Florian Bender, for his guidance and help in completing my research as well as his insight into polymers and acoustic wave devices which helped in coming to an understanding of the topic. I would also like to thank Dr. Chung Hoon Lee for his input and his time during the joint lab seminar held between the Microsensor lab group and the Nano Devices lab group. I would also like to thank my parents for their support throughout this arduous journey. Without your words of encouragement and compassion I would not have been able to reach this stage of my life. In addition, I would like to express my gratitude to my former and present labmates (Tian Newman, Jinjin Zhang, Tao Cai, Robert Lenisa, Michael McCarthy, Karthick Solthivelr, Mehbub Khan and Laura Alderson), for their advice during our lab meetings. Special thanks to Dr. Charles Wilkie and Dr. Guipeng Cai for their assistance in answering questions about plasticizers and providing me with additional reading material to broaden my knowledge of plasticizer and polymer mixing. I would finally like to thank Dr. Arnold Mensah-Brown, for introducing me to and piquing my interest in acoustic wave sensors and polymer coatings and for his guidance over the years. ii TABLE OF CONTENTS ABSTRACT .................................................................................................. ACKNOLEDGEMENTS .............................................................................. i 1 INTRODUCTION .................................................................................... 1 1.1 Problem Statement ........................................................................ 1 1.2 Overview of Chemical Sensors ........................................................ 2 1.3 Acoustic Wave Sensors ................................................................... 4 1.4 Thesis Organization ......................................................................... 5 2. REVIEW OF ACOUSTIC-WAVE AND PLASTICIZER THEORIES ........ 7 2.1 Introduction ...................................................................................... 7 2.2 SAW Sensing Principles ................................................................... 8 2.3 Plasticizers ..................................................................................... 14 2.3.1 Introduction .............................................................................. 14 2.3.2 The Lubricity Theory ................................................................ 14 2.3.3 The Gel Theory ........................................................................ 15 2.3.4 The Free Volume Theory ......................................................... 15 2.4 External Plasticizer Requirements .................................................. 16 2.4.1 Compatibility ............................................................................ 16 2.4.2 Efficiency ................................................................................. 18 iii 2.4.3 Permanence ............................................................................ 18 2.4.4 Antiplasticization ...................................................................... 19 2.4.5 Calculating Glass Transition Temperature using the Gordon and Taylor Equation ........................................................................................... 20 3 EXPERIMENTAL PROCEDURE .......................................................... 24 3.1 Introduction .................................................................................... 24 3.2 Materials Used ............................................................................... 24 3.2.1 Polymers .................................................................................. 24 3.2.2 Dioctyl Phthalate (DOP) ........................................................... 25 3.3 Equipment Used ............................................................................. 26 3.4 Experimental Procedures ............................................................... 29 3.4.1 Plasticizer Polymer Solution Preparation ................................. 29 3.4.2 Benzene Solution Preparation ................................................. 30 3.4.3 Chemical Sensing Measurements ........................................... 31 3.4.4 Data Preparation ...................................................................... 33 4 RESULTS ............................................................................................. 34 4.1 Introduction .................................................................................... 34 4.2 Measurement ................................................................................. 34 4.2.1 Polystyrene .............................................................................. 34 iv 4.2.2 Poly (Ethyl Acrylate) ................................................................ 40 4.2.3 Poly (Methyl Acrylate) .............................................................. 42 4.3 Discussion ...................................................................................... 45 5 SUMMARY, CONCLUSION AND FUTURE WORK.............................. 50 5.1 Summary ........................................................................................ 50 5.2 Conclusion ..................................................................................... 51 5.3 Future work .................................................................................... 54 BIBLIOGRAPHY ...................................................................................... 56 1 1 INTRODUCTION 1.1 Problem Statement Benzene (C 6H6) is an organic compound found as a constituent of crude oil and its refined products. Benzene is an aromatic hydrocarbon. Benzene is also derived from many industrial processes and is used as a precursor in forming other organic compounds and chemicals. Benzene has been found to be a cause of cancer in humans, particularly leukemia and cancers of other blood cells [1]. Due to benzene carcinogenic properties, the Environmental Protection Agency (EPA) set a benzene concentration limit of 5 parts per billion (ppb) or 5µg/L in drinking water sources [10]. The EPA currently requires owners of Underground Storage Tanks (UST) to perform monthly monitoring for possible releases. In the case of USTs which are younger than 10 years, only monthly inventory control and structural test of the tanks are required. In December of 2013, the EPA reported that there were 577,981 active UST regulated