The Elements of Polymer Science & Engineering PDF
Preview The Elements of Polymer Science & Engineering
THE ELEMENTS OF Polymer Science and Engineering Third Edition THE ELEMENTS OF Polymer Science and Engineering Third Edition Alfred Rudin University of Waterloo Phillip Choi University of Alberta SanDiego(cid:129)London(cid:129)Boston NewYork(cid:129)Sydney(cid:129)Tokyo(cid:129)Toronto AcademicPressisanimprintofElsevier AcademicPressisanimprintofElsevier 225WymanStreet,Waltham,MA02451,USA TheBoulevard,LangfordLane,Kidlington,Oxford,OX51GB,UK r2013ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans, electronicormechanical,includingphotocopying,recording,oranyinformationstorageandretrieval system,withoutpermissioninwritingfromthepublisher.Detailsonhowtoseekpermission, furtherinformationaboutthePublisher’spermissionspoliciesandourarrangementswith organizationssuchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency, canbefoundatourwebsite:www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyright bythePublisher(otherthanasmaybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchand experiencebroadenourunderstanding,changesinresearchmethods,professionalpractices, ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgein evaluatingandusinganyinformation,methods,compounds,orexperimentsdescribedherein. Inusingsuchinformationormethodstheyshouldbemindfuloftheirownsafetyandthesafety ofothers,includingpartiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors, assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproduct liability,negligenceorotherwise,orfromanyuseoroperationofanymethods,products, instructions,orideascontainedinthematerialherein. LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress. BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary. ISBN:978-0-12-382178-2 ForinformationonallAcademicPresspublications visitourwebsiteathttp://store.elsevier.com PrintedintheUnitedStatesofAmerica 131415 987654321 To Pearl, with thanks again for her wisdom and wit To Late Professor Rudin, for introducing me to the field of polymer science and engineering Preface Unprovided with original learning, uninformed in the habits of thinking, unskilledintheartsofcomposition,Iresolvedtowriteabook. —EdwardGibbon Since the publication of the last edition in 1999, the field of polymer science and engineering has advanced and changed considerably. The advances come from our increasing abilities to make a wide variety of polymers with tailor- made structures and/or molecular weight distribution using sophisticated polymerization techniques and to characterize the structures of such polymers at different length scales and the corresponding properties by modern analytical techniques. This trend is somewhat driven by the fact that polymers with tailor-made structures are anintegralpartofthesolutiontokeysocietalchallengesfacingussuchasenergy, water, environment, and health care areas. It is also interesting to note that high- volume polymers (e.g., polyethylene) are also made with tailor-made structures to improve their performance. The other emerging front of the field of polymer is the desire to use materials derived from renewable resources (less than 1% of the total market nowadays) due to the increasing awareness of the substantiality of usingpolymers derived frompetroleumsources.Therefore,we addedanew chap- ter (Chapter 13) to introduce the new trend of using biopolymers for various applications and what types of biopolymers have been investigated. Nevertheless, to make polymers with tailor-made structures, a deeper understanding of the molecular structure(cid:1)property relationshipis needed. Therefore, the writing ofthis edition stresses the molecular-level understanding of phenomena and processes involving the use of polymers. In this regard, throughout the textbook, if applica- ble, we explain concepts related to and/or behavior of polymers in terms of their molecular structure, particularly their conformation. In fact, a new section was added to Chapter 1 to elaborate the concept of conformation and various theoreti- cal models associated with the concept. A new chapter (Chapter 6) on the diffu- sion in polymers was added as such a topic is at the heart of many modern technologies (e.g., separation of gases using polymer membranes). In this edition, we decided not to include additional topics on polymer proces- sing and polymer degradation given the expectation that the book is used for a one semester introductory polymer course. The students should consult more spe- cialized textbooks on these topics. The book has been substantially restructured to fit the pedagogical requirement that the first six chapters mainly cover the basic concepts and models of polymer conformation (Chapter 1), definition of molecu- lar weight averages and their measurements (Chapters 2 and 3), physical and mechanical properties of polymers (Chapter 4), and polymer solutions and blends (Chapter 5). As mentioned, Chapter 6 covers an old but important topic: diffusion in polymers. The second half of the book (Chapters 7 to 13) mainly focuses on thepolymerization techniques.Inparticular, Chapter12dealswith polymerization reaction engineering. We put Chapter 13 in the second half of the book simply xvii xviii Preface because use of biopolymers requires chemical modification of natural polymers and/orpolymerization of renewable monomers. Another motivation for the third edition of the book is to improve its style to make it more comprehensible to undergraduate students studying in a variety of disciplines such as chemistry, physics, pharmacy, chemical engineering, as well as materials science and engineering. To this end, we include additional in- chapter numerical examples and new figures to illustrate the concepts involved and additional end-of-the-chapter practice problems. Most of the practice pro- blems were made using published research data and/or relevant industrial data. We believe in this way students can see how they can apply research results and industrial data to solve practical problems. A student who understands the mate- rial in the chapter should not find these problems time consuming. The problems have been formulated to require numerical rather than essay-type answers, as far as possible,since“handwaving” does notconstitute good engineeringorscience. The units in this book are not solely in SI terms, although almost all the quan- tities used are given in both SI and older units. Many active practitioners have developed intuitive understandings of the meanings and magnitudes of certain quantities in non-SI units, and it seems to be a needless annoyance to change theseparameters completelyand abruptly. The only references included here are those dealing with particular concepts in greater detail than this book. This omission is not meant to imply that the ideas that are not referenced are our own, any more than the concepts in a general chemistry textbook are those of the author of that book. We lay full claim to the mistakes, however. Mythanksgotoallthestudentswhohaveenduredthiscoursebeforeandafter the writing of the first and second editions, to the scientists and engineers whose ideas and insights form the sum of our understanding of synthetic polymers, and to the users who kindly pointed out errors in the previous editions. Some of the present students of the junior author (P. C.) made important contribution to this edition. In particular, Abolfazl Noorjahan and Nicole Lee Robertson helped write and revise Chapter 6 and Chapter 13, respectively, and drew most of the figures therein. Choon Ngan Teo helped prepare new examples and draw new figures in Chapters 3 and 5 and renumbered many equations, figures, tables, and sections ofa number ofchapters. I (P. C.) express my sincere gratitude to the senior author (A. R.) for his trust in me as well as his encouragement for the preparation of this edition. I also express most sincere thanks to my wife, Deborah, and to my children, Calvin and Samantha, who have given me unlimited love, support, and understanding throughout myacademic life. Alfred Rudin and Phillip Choi In Memoriam for Alfred Rudin (1924–2011) I took my first polymer science and engineering course from Dr. Alfred Rudin in the early 1990s. In the class, we used the first edition of this book. It was pub- lished in 1982 and was a result of a correspondence course given by Alf to “dis- tance” students, mostly part-time students from local industry, at the University of Waterloo in Waterloo, Ontario. Since the book had been adopted by many uni- versities, he updated it in 1999 (second edition). About two years ago, Alf approached me to ask if I would be interested in doing the third edition. I was flattered and agreed on the spot. Here, I would like to take this opportunity to expressmy most sincere gratitudeto Alf for his trust inme. Unfortunately, during the preparationofthisedition, Alf passedaway. Itwas aloss tothe polymer com- munity towhich Alf had contributed significantly. Dr. Alfred Rudin was born in Edmonton, Alberta, on February 5, 1924. He grew up in a small coal-mining town of Nordegg, that is about 200km southwest of Edmonton. When he was 17, he enlisted in the Canadian Army as an underage soldier and served for the Signal Corps for 31/ years. He went from the Army to 2 the University of Alberta in Edmonton to further his education. He graduated from an honors chemistry program in 1949. In the same year, Alf married Pearl and went to Northwestern University in Chicago, Illinois, where he did his doc- toral work with Prof. HermanPines inthe area of catalytic organic chemistry. In1952,Alf,withPearl,returnedtoCanadaandstartedtoworkfortheCentral Laboratory of Canadian Industries Limited (CIL) in McMasterville, Quebec, in a varietyofresearchandmanagerialpositions.In1967,hemovedtotheDepartment of Chemistry at the University of Waterloo as a professor and stayed there for the rest of his career. Alf authored and co-authored almost 300 refereed publications and was granted 25 patents. Over the course of his academic career, Alf and Dr. Kenneth F. O’Driscoll, a chemical engineering professor, cofounded the Institute for Polymer Research at the University of Waterloo. Today, the Institute includes about 20 professors and many corporate members. In the late 1970s, Alf and Dr. Alan Plumtree, a mechanical engineering professor, upon a request from the International Development Research Centre, designed a pump that is suitable for small villages in developing countries. The so-called Waterloo Pump that they designed is inexpensive, corrosion resistant, and easily repairable by people living in developing countries. Today, millions of people living in developing countries gettheirwaterusingsuchpumps. Alf was a remarkable mentor who inspired many students. In my view, he had the passion and the unique abilities and insights to inspire and to advise students xix xx In Memoriam for Alfred Rudin with very diverse backgrounds. In fact, all of his former graduate students really appreciated his hints, comments, and advice on both technical and non-technical matters. Owing to his thoughtful advice, many of us have embarked on enjoyable and successful careers. Alf was a life-long learner. I witnessed him learning how to use a computer in his mid-sixties. In fact, Alf prepared the soft version of the entire manuscriptof the secondedition ofthis book onhis own. Alf received many awards for his accomplishments in his career. In particular, he received the Protective Coatings Award of the Chemical Institute of Canada and shared a Roon Award of the Federation of Societies for Coatings Technology in 1988. He was the first recipient of the Macromolecular Science and Engineering Award of the Chemical Institute of Canada in 1989. Alf was a fellow of the Chemical Institute of Canada, the Royal Society of Canada, and the Federation of Societies for Coatings Technology. He was named Distinguished Professor Emeritus at the University ofWaterloo. After Alf finished with his last graduate student, he and Pearl moved to Toronto to enjoy their city life and to spend more time with their three sons, Jonathan, Jeremy, and Joel, and their families. Alf was a devoted storytelling grandfather of Shira, Jacob, and Arielle. I will always remember Alf as a great advisor with broad scientific knowledge andas akind person ofgood humor. CHAPTER 1 Introductory Concepts and Definitions Knowledgeisatreasure,butpracticeisthekeytoit. —ThomasFuller,Gnomologia 1.1 Some Definitions Some basic concepts and definitions of terms used in the polymer literature are reviewed in this chapter. Much of the terminology in current use in polymer sci- ence has technological origins, and some meanings may therefore be understood by convention as well as by definition. Some of these terms are included in this chapter since a full appreciation of the behavior and potential of polymeric mate- rials requires acquaintance with technical developments as well as with the more academic fundamentals of the field. An aim of this book is to provide the reader with the basic understanding and vocabulary for further independent study in both areas. Polymer technology is quite old compared to polymer science. For example, natural rubber was first masticated to render it suitable for dissolution or spread- ing on cloth in 1820, and the first patents on vulcanization appeared some twenty years later. About another one hundred years were to elapse, however, before it was generally accepted that natural rubber and other polymers are composed of giant covalently bonded molecules that differ from “ordinary” molecules primar- ily only in size. (The historical development of modern ideas of polymer constitu- tion is traced by Flory in his classical book on polymer chemistry [1], while Brydson [2] reviews the history of polymer technology.) Since some of the terms we are going to review derive from technology, they are less precisely defined than those the reader may have learned in other branches of science. This should not be cause for alarm, since all the more important definitions that follow are clear inthe contexts inwhich they are normallyused. 1.1.1 Polymer Polymer means “many parts” and designates a large molecule made up of smaller repeating units. Thus the structure ofpolystyrene can be written 1 TheElementsofPolymerScience&Engineering. ©2013ElsevierInc.Allrightsreserved. 2 CHAPTER 1 Introductory Concepts and Definitions H H H H ~ CH C CH C CH C CH C ~ 2 2 2 2 1-1 Polymers generally have molecular weights greater than about 5000 but no firm lower limit need be defined since the meaning of the word is nearly always clear from itsuse. The word macromolecule is a synonym for polymer. 1.1.2 Monomer A monomer is a molecule that combines with other molecules of the same or dif- ferent type to form a polymer. Acrylonitrile, CHQCHCN, is the monomer for 2 polyacrylonitrile: H H H H ~ CH C CH C CH C CH C ~ 2 2 2 2 CN CN CN CN 1-2 whichis the basicconstituent of“acrylic” fibers. 1.1.3 Oligomer Anoligomerisalow-molecular-weightpolymer.Itcontainsatleasttwomonomer units.Hexatriacontane (n-CH —(CH ) —CH )is an oligomer ofpolyethylene 3 2 29 3 CH CH CH CH CH CH CH CH CH : 2 2 2 2 2 2 2 2 2 1-3 Generally speaking, a species will be called polymeric if articles made from it have significant mechanical strength and oligomeric if such articles are not strong enough to be practically useful. The distinction between the sizes of oligomers and the corresponding polymers is left vague, however, because there is no sharp transition inmost properties ofinterest. The terms used above stem from Greek roots: meros (part), poly (many), oligo (few), andmono (one).
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