INCORPORATION of LESS TOXIC ANTIFOULING COMPOUNDS INTO SILICONE COATINGS to STUDY THEIR RELEASE BEHAVIORS a Dissertation Present
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INCORPORATION OF LESS TOXIC ANTIFOULING COMPOUNDS INTO SILICONE COATINGS TO STUDY THEIR RELEASE BEHAVIORS A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirement for the Degree Doctor of Philosophy Abdulhadi Abdullah Al-Juhni August, 2006 INCORPORATION OF LESS TOXIC ANTIFOULING COMPOUNDS INTO SILICONE COATINGS TO STUDY THEIR RELEASE BEHAVIORS Abdulhadi Abdullah Al-Juhni Dissertation Approved: Accepted: Advisor Department Chair Dr. Bi-min Zhang Newby Dr. Lu-Kwang Ju Committee Member Dean of the College Dr. George G. Chase Dr. George K. Haritos Committee Member Dean of the Graduate School Dr. Lu-Kwang Ju Dr. George R. Newkome Committee Member Date Dr. Gerald W. Young Committee Member Dr. Teresa J. Cutright ii ABSTRACT Biofouling has always caused serious problems, including increased fuel consumption and maintenance costs for vessels, to the naval industry. The use of toxic antifouling compounds to combat the organisms attached and accumulated on the surface of submerged structures has been common. However, the current ban on the application of conventional tin-based antifouling compounds has accelerated the research to seek for less toxic alternatives. In this study, four much less-toxic antifouling compounds (sodium benzoate, benzoic acid, capsaicin, and tannic acid), as compared to tin-based antifoulants, were incorporated into two types of silicone coatings (Sylgard® 184 and RTV11) by applying a solvent-blending technique. These compounds were proven to be effective against some bacterial growth and attachments; however, a systematic study on the miscibility and the release of these compounds from the coatings is lacking. Therefore, the focus of the current study is to correlate the miscibility of the compounds in the coatings and their release rates in water, for the purpose of controlling the release of the compounds. It was found that benzoic acid and capsaicin formed large crystals inside the coating; whereas sodium benzoate and tannic acid were able to form small aggregates inside the coatings. The magnitude of the leaching of the four compounds was in the iii order of: benzoic acid > capsaicin > sodium benzoate > tannic acid. The solvent-assisted blending technique was adequate for the cases of sodium benzoate and tannic acid whereas it was not suitable for benzoic acid and capsaicin. Sodium benzoate/Sylgard® 184 coating was then selected as the model system to obtain the miscibility-release relationship. The preparation conditions were found to have important effects on the morphological structure and final distribution of sodium benzoate in silicone, hence the leaching. The minimum average aggregate size obtained was ~ 3 µm, which had resulted in the lowest value for the steady leaching rate of ~ 0.1 µg/cm2/day. Empirical correlations were obtained between the aggregate size as well as the matrix loading of sodium benzoate and the leaching rate. It was found that increasing the aggregate size had a sharp effect on the increase of the leaching rate, whereas increasing the matrix loading (up to 5 wt. %) had a mild effect on the leaching rate. The current study did show that the solvent-assisted blending technique can be an efficient approach for constructing the miscibility-release correlations. Both thermodynamic analysis and experimental observations showed that sodium benzoate has limited solubility in the Sylgard® 184 coating. This, combined with the mass transfer analysis of the leaching, led us to confirm that the release mechanism of the monolithic sodium benzoate/silicone coatings generated via the solvent-assisted blending technique is mainly by the diffusion of the compound through water-filled pores and constricted channels within the matrix, not through the continuum of the polymer phase. iv ACKNOWLEDGEMENTS I would like to thank my advisor Dr. Bi-min Zhang Newby, for consistently and patiently providing me with continues guidance, informative discussion, and educational help throughout my PhD research. I would like also to thank my committee members; Dr. Teresa Cutright, Dr. George Chase, Dr. Lu-Kwang Ju, and Dr. Gerald Young, for their informative discussion and valuable comments and suggestion. I would like also to thank Dr. Cutright and her research group for assisting me in bacterial attachment study. I would like also to thank Dr. Sung-Hwan Choi for the AFM scanning. Thanks are also due to all members of my research group, for being helpful during my entire study. I want to express my deep thanks to the Ministry of Higher Education, Saudi Arabia, for granting me a full scholarship to get my PhD degree, without their financial support it would be difficult to accomplish this study. Appreciations are also due to the Department of Chemical and Biomolecular Engineering, the Ohio Sea Grant (Project: R/MB-2) and the Ohio Board of Regents, for partial financial support of my research project. Finally, I would like to express my deep gratitude to my wife Fatimah, being patient here with me and supporting me to accomplish my objective, and to my parents, far away and being patient waiting for me. v TABLE OF CONTENTS Page LIST OF TABLES………………………………………………………………………...x LIST OF FIGURES……………………………………………………………………...xii CHAPTER I. INTRODUCTION………………………………….…………………………...........1 1.1 Introduction…...…………………………………………………………………1 1.2 Importance and scope of the study…………….………………………………...5 1.3 Objectives…………………………………….………………………….............6 1.4 Dissertation outline…………………………...………………………………….7 II. LITERATURE REVIEW………………………………….…………………………8 2.1 Biofouling and biofilms formation…..…………………………………………..8 2.2 Biofouling controls…..…………………………………………………………10 2.2.1 Conventional toxic antifouling coatings……………………………...11 2.2.2 Silicone foul-release coatings………….……………………………..12 2.2.3 Less-toxic antifoulants…………………….………………………….16 2.3 Antifoulant-matrix miscibility………………………………………………….23 2.4 Modeling of the antifoulants release from polymeric matrices…….…………..33 2.4.1 Active compounds with high solubility in the matrix………………...35 vi 2.4.2 Active compounds with low solubility in the matrix………..………..38 2.4.3 Leaching behaviors of marine antifouling paints……………………..41 III. EXPERIMENTAL APPROACH………..………………………………………….46 3.1 Materials…….………………………………………………………………….46 3.2 Sample preparation……………………………………………………………..48 3.3 Sample processing……………………………………………………………...53 3.4 Characterization techniques…………………………………………………….57 3.4.1 Contact angles technique.…………………………………………….57 3.4.2 The stress - strain technique………….……………………………….59 3.4.3 The JKR technique…………………………………………………....60 3.4.4 Optical microscopy…………………………………………………...61 3.4.5 Scanning probe microscopy………….……………………………….63 3.4.6 High performance liquid chromatography (HPLC)…………………..64 IV. RESULTS AND DISCUSSION FOR SODIUM BENZOATE– BASED COATINGS……………………………………………………………….66 4.1 Effect of sodium benzoate on surface and bulk properties of silicones….…….66 4.1.1 Effect on wettability…………………………………………………..67 4.1.2 Effect on elastic modulus……………………………………………..71 4.2 Miscibility of NaB in silicones……...………………………………………….73 4.2.1 Effect of composition of the mixed solvent…………………………..74 4.2.2 Effect of solvent/polymer ratio……...………………………………..78 4.2.3 Effect of NaB matrix loading……….………………………………...78 4.3 Thermodynamic analysis for the miscibility study ….………………………...83 4.3.1 Prediction by the Flory-Huggins theory……………………………....83 vii 4.3.2 Modification of the Flory-Huggins theory to include electrostatic contribution and concentration-dependent interaction parameters…..………………………………………………………...86 4.3.3 Comparison between the theoretical miscibility trends and the experimental morphology trends……………………………………...95 4.4 Leaching evaluation……...…………………………………………………....100 4.4.1 Effect of composition of the mixed solvent………………………....100 4.4.2 Effect of solvent/polymer ratio……………………………………...102 4.4.3 Effect of NaB matrix loading……...………………………………...102 4.4.4 Effect of type of the silicone matrix………………………………....105 4.4.5 Empirical correlations for the leaching rate of NaB from Sylgard® 184…………………………………………………..108 4.4.6 Effects of continuous stirring and water replacement ………..……..111 4.5 Mass transfer analysis for the leaching study………..………………………..114 4.5.1 Simplified mass transfer model……………………………………...114 4.5.2 Limitation of the simplified mass transfer model…………………...130 4.6 Bacterial attachment evaluations............……………………………………...138 V. RESULTS AND DISCUSSION FOR BENZOIC ACID AND CAPSAICIN- BASED COATINGS…............................................................................................144 5.1 Effects of the compounds on coating’s properties…………...……………….144 5.1.1 Effect of benzoic acid…………………………….............................144 5.1.2 Effect of capsaicin…………………………………………………...147 5.2 Miscibility of the compounds in silicones…….……………………………....150 5.2.1 Miscibility of benzoic acid…………………………..........................150 5.2.2 Miscibility of capsaicin……………………………………………...154 5.3 Leaching evaluation…………………………………………………………..157 viii 5.3.1 Leaching of benzoic acid……………………………........................157 5.3.2 Leaching of capsaicin……………………………………………….159 5.4 Bacterial attachment evaluations for capsaicin-RTV11 coatings.……………163 5.4.1 Effect of immersion in water on coating’s properties………….…...163 5.4.2 Bacterial attachment evaluations……………………………………169 VI. RESULTS AND DISCUSSION FOR TANNIC ACID-BASED COATINGS…...171 6.1 Effect of tannic acid on coating’s properties……………………………….....171 6.2 Miscibility of tannic acid in silicones……………………………………........173