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ABSTRACT FU, SHA. Studies on Dyeing

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ABSTRACT FU, SHA. Studies on Dyeing ABSTRACT FU, SHA. Studies on Dyeing Cationized Cotton. (Under the direction of Dr. Peter Hauser and Dr. David Hinks). Even with the extensive research and rapid development of synthetic fibers, cotton is still the dominant raw material due to its unique combination of properties, especially the natural comfort. Based on its cellulosic structure, cotton has good reactivity or affinity for a variety of dyes. With advantages in wet fastness properties and a wide range of hue, reactive dyes are one of the most commonly used dyes for cotton coloration. However, the conventional reactive dyeing process is plagued with a high degree of salt utilization and colored effluent due to unexhausted, unfixed, and hydrolyzed dyestuffs. This is caused by the same anionic charges of both reactive dyes and cotton in water, resulting in poor affinity of most reactive dyes for cotton. With the need for cleaner, cost-effective, and colorfast textile products, innovative technologies and improved processes have been developed for cotton coloration. As an important root to obtaining the desired dyeing performance with existing dyes, chemical modification of cotton fiber to impart cationic charges have been widely researched in recent years. By introducing cationic groups into cotton fibers, the affinity of anionic dyes for cotton was significantly improved, which allows the dyeing of cotton fabrics without salt and up to 100% reactive dye utilization. With less chemical, water, and energy consumption, the dyeing of cationized cotton is a potentially environmentally responsible process. The most commonly used cationic agent is 3-chloro-2-hydroxypropyl trimethylammonium chloride (CHPTAC) due to its relatively good reaction efficiency and low cost. Cationization can also be used with other treatment methods to further improve the dyeing performance and other properties of cotton fabrics. In this research, cationization with CHPTAC was used in combination with mercerization to obtain ultra-deep reactive dyeing on cotton. The effects of mercerization and cationization degrees on dyeing performance and colorfastness properties were evaluated. Further, the influence of liquor ratio and dyestuff in producing ultra-deep black dyeing on mercerized cationized cotton was also investigated and compared with conventional reactive dyeing. Results showed that the ultra-deep black shade on mercerized cationied cotton was not obtainable using uncationized cotton, even with very low liquor ratio and drastically increased dye amount. With high concentrations of dyes applied, levelness of dyeing is not a critical issue for ultra-deep reactive dyeing on cationized cotton. However, when shades with light to medium depth are required, reactive dyeing of cationized cotton may suffer from the problem of poor levelness due to ionic attractions between anionic dyes and cationic cotton fibers. Thus, the influence of temperature, dye structure, addition of soda ash, and leveling agents on dyeing kinetics and levelness were evaluated for cationized cotton. Suggestions on dyeing procedures and chemical recipes were made for different dye structures. With controlled dyeing process and effective leveling agents, dye strike rate and dyeing levelness of cationized cotton were effectively controlled. Finally, a comparative life-cycle analysis of cationization dyeing versus conventional reactive dyeing of cotton was conducted to evaluate the environmental impacts of applying cationization. Among the six environmental impact categories assessed, the conventional reactive dyeing system has higher environmental impacts in half of the categories, including global warming, acidification, and ecotoxicity potential. For the cationization dyeing system, the use of CHPTAC for cationization caused high impacts in eutrophication and human health. Due to the limitations in database and assessment methodologies, there is no firm conclusion on which dyeing system is more environmentally beneficial. Feasible cleaner production proposals were suggested for both dyeing systems. © Copyright 2016 by Sha Fu All Rights Reserved Studies on Dyeing Cationized Cotton by Sha Fu A dissertation submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Fiber and Polymer Science Raleigh, North Carolina 2016 APPROVED BY: _______________________________ _______________________________ Dr. Peter Hauser Dr. David Hinks Co-chair of Advisory Committee Co-chair of Advisory Committee _______________________________ _______________________________ Dr. Warren Jasper Dr. Joseph DeCarolis DEDICATION This work is dedicated to my grandparents. ii BIOGRAPHY Sha Fu was bone on June 22nd, 1991 in Zhangshu, Jiangxi Province of China. She is the only daughter of Qingzheng Fu and Yanwen Du. She got her bachelor degree from Donghua University, Shanghai in 2012. By attending the “3+X” program, Sha entered North Carolina State University and got her Master degree in Textile Chemistry in 2013. After that, she continued her study and research in the Fiber and Polymer Science Doctoral program at North Carolina State University. iii ACKNOWLEDGMENTS First, I would like to express my sincere thanks my committee members for their help during my research, especially my co-advisors, Dr. Peter Hauser and Dr. David Hinks. Their patience and guidance throughout my research helped me grow a lot. I also want to thank Dr. Warren Jasper for his instruction and help with the HueMetrix Monitor. I learned a lot from Dr. Joseph DeCarolis on life-cycle analysis and I want to thank him for being my committee member and offering more help on that aspect. Besides, I really appreciate Cotton Inc. and HanesBrands for their support to my research projects, especially the help from Dr. Matthew Farrell. As well, I am very thankful to Mr. Jeffrey Krauss and Mrs. Judy Elson for their kindness and help with my experiments. Last but not least, I want to give my special thanks to my parents and all my dear friends for just being with me. iv TABLE OF CONTENTS LIST OF TABLES ................................................................................................................. viii LIST OF FIGURES ................................................................................................................. x CHAPTER 1 INTRODUCTION ............................................................................................ 1 1.1 Background .......................................................................................................... 1 1.2 Research Objectives ............................................................................................. 3 1.3 Research Outline .................................................................................................. 3 CHAPTER 2 LITERATURE REVIEW ................................................................................ 5 2.1 Coloration of Cotton ............................................................................................ 5 2.1.1 Introduction ................................................................................................... 5 2.1.2 Basic Chemistry of Cotton Coloration .......................................................... 6 2.1.3 Fiber Reactive Dyes ...................................................................................... 7 2.1.4 Direct Dyes ................................................................................................. 13 2.1.5 Azoic Dyes .................................................................................................. 14 2.1.6 Vat Dyes ...................................................................................................... 16 2.1.7 Sulfur Dyes ................................................................................................. 17 2.1.8 Developments in Cotton Coloration ........................................................... 18 2.2 Cationization of Cotton ...................................................................................... 22 2.2.1 Reasons for Cationization ........................................................................... 22 2.2.2 Cationic Reagents ....................................................................................... 22 2.2.3 Cationization with CHPTAC ...................................................................... 35 2.3 Mercerization of Cotton ..................................................................................... 42 2.3.1 Changes in Structure of Cotton on Mercerization ...................................... 42 2.3.2 Changes in Properties of Cotton on Mercerization ..................................... 46 2.3.3 Control Variables and Machinery for Mercerization .................................. 48 2.3.4 Evaluation of Mercerization Effects ........................................................... 52 2.3.5 Mercerized Cationized Cotton .................................................................... 53 2.4 Kinetics of Cotton Dyeing with Reactive Dyes ................................................. 54 2.4.1 Basic Dyeing Theory .................................................................................. 54 2.4.2 Dyeing of Cationized Cotton ...................................................................... 61 2.4.3 Dyebath Monitoring .................................................................................... 66 v CHAPTER 3 DEEP DYEING ON MERCERIZED CATIONIZED COTTON .............. 74 3.1 Influence
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