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Polymeric Materials in Corrosion Inhibition Fundamentals and Applications This pageintentionallyleftblank Polymeric Materials in Corrosion Inhibition Fundamentals and Applications Saviour A. Umoren Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia Moses M. Solomon Department of Chemistry, Covenant University, Ota, Nigeria Viswanathan S. Saji Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia Elsevier Radarweg29,POBox211,1000AEAmsterdam,Netherlands TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates Copyright©2022ElsevierInc.Allrightsreserved. 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Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluating andusinganyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuch informationormethodstheyshouldbemindfuloftheirownsafetyandthesafetyofothers,including partiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assume anyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability, negligenceorotherwise,orfromanyuseoroperationofanymethods,products,instructions,orideas containedinthematerialherein. ISBN:978-0-12-823854-7 ForInformationonallElsevierpublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:MatthewDeans AcquisitionsEditor:EdwardPayne EditorialProjectManager:GabrielaD.Capille ProductionProjectManager:PrasannaKalyanaraman CoverDesigner:VictoriaPearson TypesetbyMPSLimited,Chennai,India Contents Aboutthe authors....................................................................................................xv Preface..................................................................................................................xvii Acknowledgments..................................................................................................xxi PART I The Fundamentals................................................... 1 CHAPTER 1 Basic polymer concepts I.............................................3 1.1 Introduction....................................................................................3 1.2 Classification ofpolymers.............................................................4 1.2.1 Classification based onsource............................................4 1.2.2 Classification based onstructure of polymers...................4 1.2.3 Classification based onmode ofpolymerization...............7 1.2.4 Classification based onmolecular forces...........................8 1.3 Generalproperties ofpolymers....................................................11 1.3.1 Thermal properties............................................................11 1.3.2 Mechanical properties.......................................................13 1.3.3 Solubility properties..........................................................13 1.3.4 Optical properties..............................................................14 1.4 Polymerization reactions..............................................................14 1.4.1 Chain-growth oradditionpolymerization reactions.........14 1.4.2 Step-growth or condensation polymerization reaction.....23 1.4.3 Ionicpolymerization.........................................................25 1.4.4 Coordinationpolymerization............................................31 1.4.5 Controlled radical polymerization....................................35 1.5 Polymerization techniques...........................................................41 1.5.1 Gas phase polymerization.................................................42 1.5.2 Bulk polymerization..........................................................42 1.5.3 Solution polymerization....................................................44 1.5.4 Suspension polymerization...............................................45 1.5.5 Emulsion polymerization..................................................45 1.5.6 Solidphase polymerization...............................................47 Further reading............................................................................48 CHAPTER 2 Basic polymer concepts II..........................................49 2.1 Molecular weight and molecularweight distribution.................49 2.1.1 Methodsof molecularweightdetermination...................51 v vi Contents 2.2 Copolymerization.........................................................................57 2.2.1 Types of copolymers.........................................................58 2.2.2 Copolymer composition....................................................59 2.3 Biodegradable polymers...............................................................64 2.4 Uses ofpolymers..........................................................................65 2.4.1 Polymersincorrosion control...........................................66 2.4.2 Polymersas scale inhibitors.............................................66 2.4.3 Polymersas adsorbents.....................................................68 2.4.4 Polymersinbiomedical applications................................72 2.4.5 Polymersfor enhanced oilrecovery.................................72 2.4.6 Other applications.............................................................75 References....................................................................................78 Further reading............................................................................81 CHAPTER 3 Basic concepts of corrosion ......................................83 3.1 Introduction..................................................................................84 3.2 Definition......................................................................................84 3.3 Types ofcorrosion........................................................................84 3.3.1 Uniform orgeneral corrosion.........................................84 3.3.2 Galvanic orbimetallic corrosion....................................85 3.3.3 Pitting corrosion..............................................................85 3.3.4 Crevice corrosion............................................................85 3.3.5 Intergranular corrosion....................................................86 3.3.6 Dealloying.......................................................................86 3.3.7 Flow-assisted corrosion...................................................86 3.3.8 Stress corrosion cracking................................................87 3.3.9 Microbiologically influenced corrosion.........................87 3.3.10 Filiform corrosion...........................................................87 3.3.11 Exfoliation.......................................................................88 3.3.12 Corrosion fatigue.............................................................88 3.3.13 Hydrogen embrittlement corrosion.................................88 3.3.14 Fretting corrosion............................................................88 3.3.15 Sweet and sour corrosion................................................89 3.3.16 Top ofthe line corrosion................................................90 3.4 Factors influencing corrosion.......................................................91 3.4.1 Physical factors.................................................................91 3.4.2 Chemicalfactors...............................................................92 3.4.3 Biological factors..............................................................92 3.4.4 Surface area effect............................................................92 3.5 Consequences andcost of corrosion............................................92 3.6 Theoriesofcorrosion...................................................................93 Contents vii 3.7 Corrosionmitigation approaches.................................................96 3.7.1 Protective coatings............................................................96 3.7.2 Material selection anddesign...........................................98 3.7.3 Cathodic protection...........................................................98 3.7.4 Corrosioninhibitors..........................................................98 References....................................................................................99 Further reading..........................................................................102 CHAPTER 4 Fundamentals of corrosion inhibition......................103 4.1 Introduction................................................................................103 4.2 Corrosioninhibitors....................................................................104 4.3 Classes ofcorrosion inhibitors...................................................104 4.3.1 Passivating inhibitors......................................................104 4.3.2 Cathodic inhibitors..........................................................105 4.3.3 Organic inhibitors...........................................................105 4.3.4 Precipitation inhibitors....................................................106 4.3.5 Volatile corrosion inhibitors...........................................106 4.3.6 Adsorption inhibitors......................................................106 4.3.7 Surface reactionproduct inhibitors................................106 4.3.8 Interphase inhibitors........................................................107 4.3.9 Interface inhibitors..........................................................107 4.4 Factors affecting corrosion inhibitor effectiveness...................107 4.5 Mechanism of corrosion inhibition............................................109 4.6 Techniques for corrosion rate and inhibitionefficiency determination..............................................................................110 4.6.1 Chemical techniques.......................................................110 4.6.2 Electrochemical methods................................................114 4.7 Surface analysismethods...........................................................122 4.7.1 Atomic force microscopy................................................122 4.7.2 X-ray photoelectron spectroscopy..................................122 4.7.3 Scanning electron microscopy........................................123 4.7.4 Energy dispersive spectroscopy......................................124 References..................................................................................125 Further reading..........................................................................127 Part II Natural Polymers in Corrosion Inhibition............ 129 CHAPTER 5 Chitosan.....................................................................131 5.1 Introduction................................................................................131 viii Contents 5.2 Synthesis andproperties of chitosan.........................................132 5.2.1 Preparation......................................................................132 5.2.2 Properties.........................................................................134 5.3 Application of chitosanas corrosion inhibitor indiverse media..........................................................................................136 5.3.1 Acid media......................................................................137 5.3.2 Other corrosivemedia.....................................................142 5.4 Enhancementofcorrosion inhibition performance of chitosan..................................................................................145 5.4.1 Combinationfor synergistic effect.................................145 5.4.2 Modificationby compositing..........................................147 References..................................................................................148 CHAPTER 6 Chitosan derivatives.................................................155 6.1 Introduction................................................................................155 6.1.1 Synthesisand characterizationof chitosan derivatives.......................................................................156 6.2 Application of chitosanderivatives ascorrosion inhibitors indifferent media.......................................................................169 6.2.1 Chitosan derivativeswith diverse heteroatoms..............171 6.2.2 Chitosan Schiff bases incorrosioninhibition................175 6.2.3 Other chitosan derivativesincorrosion inhibition.........175 6.3 Enhancementofcorrosion inhibition by chitosan derivatives...................................................................................177 References..................................................................................181 CHAPTER 7 Cellulose and its derivatives....................................187 7.1 Introduction................................................................................187 7.1.1 Carboxymethyl cellulose................................................189 7.2 Other cellulose derivatives.........................................................197 7.2.1 Other cellulose derivativesas corrosioninhibitors........201 7.2.2 Enhancement of corrosioninhibition performance ofothercellulose derivatives..........................................201 References..................................................................................204 CHAPTER 8 Natural gums and their derivatives..........................209 8.1 Introduction................................................................................209 8.1.1 Classification ofgums....................................................211 8.2 Application of gums ascorrosion inhibitors.............................213 Contents ix 8.2.1 Gum Arabic.....................................................................213 8.2.2 Gum Arabic incorrosioninhibition...............................216 8.3 Guar gum....................................................................................221 8.3.1 Preparation......................................................................222 8.3.2 Properties.........................................................................223 8.3.3 Guargum incorrosioninhibition...................................224 8.4 Xanthan gums.............................................................................225 8.4.1 Xanthan gums in corrosion inhibition............................227 8.5 Gellan gum.................................................................................230 8.5.1 Preparation......................................................................230 8.5.2 Properties.........................................................................231 8.5.3 Gellan gum incorrosion inhibition................................231 References..................................................................................232 CHAPTER 9 Other natural gums and gum modifications.............237 9.1 Introduction................................................................................237 9.2 Carrageenan................................................................................237 9.2.1 Carrageenanin corrosion inhibition...............................240 9.3 Other exudategums in corrosion inhibition..............................240 9.4 Enhancement ofthe corrosion inhibition performance ofgums.......................................................................................248 9.4.1 Chemical modification....................................................248 9.4.2 Synergism........................................................................250 References..................................................................................251 CHAPTER 10 Pectin and derivatives..............................................255 10.1 Introduction................................................................................255 10.2 Classification ofpectin...............................................................256 10.3 Sourcesand preparation ofpectin.............................................257 10.4 Properties ofpectin....................................................................259 10.5 Application of pectin as acorrosion inhibitor...........................261 10.6 Enhancement ofthe corrosion inhibition performance ofpectin......................................................................................266 References..................................................................................267 CHAPTER 11 Alginate and its derivatives......................................271 11.1 Introduction................................................................................271 11.2 Preparation ofalginate...............................................................271 11.3 Properties ofalginates................................................................274