Analysis and Deformulation of Polymeric Materials Paints, Plastics, Adhesives, and Inks TOPICS IN APPLIED CHEMISTRY Series Editors: Alan R. Katritzky, FRS Kenan Professor ofChemistry University of Florida, Gainesville, Florida Gebran J. Sabongi Laboratory Manager, Encapsulation Technology Center 3M Company, St. Paul, Minnesota Current volumes in theseries: ANALYSISANDDEFORMULATION OF POLYMERIC MATERIALS Paints, Plastics, Adhesives, and Inks Jan W. Gooch CHEMISTRY AND APPLICATIONS OF LEUCO DYES Edited by Ramaiah Muthyala FROM CHEMICAL TOPOLOGY TO THREE-DIMENSIONAL GEOMETRY Edited by Alexandru T. Balaban LEAD-BASED PAINT HANDBOOK Jan W. Gooch ORGANOFLUORINE CHEMISTRY Principles and Commercial Applications Edited by R. E. Banks, B. E. Smart, and J. C. Tatlow PHOSPHATE FIBERS Edward J. Griffith POLY(ETHYLENE GLYCOL) CHEMISTRY Biotechnical and Biomedical Applications Edited by J. Milton Harris RADIATION CURING Science and Technology Edited by S. Peter Pappas RESORCINOL Its Uses and Derivatives Hans Dressler TARGET SITES FOR HERBICIDE ACTION Edited by Ralph C. Kirkwood AContinuation Order Planisavailable for this series. Acontinuationorderwill bring delivery ofeachnew volumeimmediatelyupon publication. Volumesarebilled only upon actualshipment.For further informa- tion please contactthe publisher. Analysis and Deformulation of Polymeric Materials Paints, Plastics, Adhesives, and Inks Jan W. Gooch Polymers and Coatings Consultant Atlanta. Georgia KLUWER ACADEMIC PUBLISHERS New York / Boston / Dordrecht / London / Moscow eBook ISBN: 0-306--46908-1 Print ISBN: 0-306-45541-2 ©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©1997 Kluwer Academic / Plenum Publishers New York All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: http://kluweronline.com and Kluwer's eBookstore at: http://ebooks.kluweronline.com Preface This book is designed for the chemist, formulator, student, teacher, forensic scientist, or others who wish to investigate the composition of polymeric materials. Theinformationwithinthesepagesisintendedtoarmthereaderwiththenecessary workingknowledgetoanalyze,characterize,anddeformulatematerials. ThestructureoftheContentsisintendedtoassistthereaderinquicklylocating the subject ofinterestand proceed to it witha minimum ofexpended time and effort. The Contentsprovides an outlineofmajortopics andrelevantmaterials charac- terizedforthereader’sconvenience.Anintroductiontoanalysisanddeformulation isprovidedinChapter1 toacquaintthereaderwithanalyticalmethodsandtheir applications. Extensive references are provided as additional sources ofinforma- tion.AlltablesarelocatedintheAppendix,beginningonp.235. GUIDE FOR USE Thisis apracticalbookstructuredtoefficientlyusethereader’s timewitha minimumeffortofsearchingforentriesandinformationbyfollowingthesebrief instructions: 1. SearchtheContentsand/orIndexforasubjectwithinthetext. 2. Analysis/deformulation principles are discussed at the outset to familiarize the reader with analysis methods and instruments; followed byformula- tions, materials,andanalysisofpaint,plastics,adhesives,andinks; and finallyreformulation methods totesttheresultsofanalysis. 3. Materials and a wide assortment of formulations are discussed within the text by chapter/section number. 4. Materials are referredtobyvarious names (trivial, trade, andscientific), and these are listed intablesandcross-referencedto aid thereader. v vi Preface ACKNOWLEDGMENTS I wish to thank the following people for their contributions to this book: Lisa Detter-Hoskin; Garth Freeman; John Sparrow; Joseph Schork; Gary Poehlein, Kash Mittal; John Muzzy; Paul Hawley; Ad Hofland; Tor Aasrum; James Johnson; Linda, Sonja, Luther, and LottieGooch. Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List of Figures xvii . 1 DeformulationPrinciples 1.1. Introduction ...................................... 1 1.2. Characterization of Materials .......................... 2 1.3. Formulation andDeformulation ........................ 2 . 2 SurfaceAnalysis 2.1. LightMicroscopy(LM) .............................. 7 2.1.1. Fundamentals ................................ 7 2.1.2. Equipment.................................... 12 2.1.3. Applications .................................. 12 2.2. ElectronMicroscopy(EM) ............................ 13 2.2.1. Fundamentals ............................... 13 2.2.2. Equipment.................................. 17 2.2.3. Applications .................................. 18 2.3. Energy-DispersiveX-RayAnalysis(EDXRA) .............. 19 2.3.1. Fundamentals ............................... 19 2.3.2. Equipment ................................... 21 2.3.3, Applications ................................ 21 2.4. ElectronProbeMicroanalysis(EPM) .................... 21 2.4.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.4.2. Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.4.3. Applications ................................. 22 2.5. AugerSpectroscopy(AES)........................... 24 2.5.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.5.2. Equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 vii viii Contents 2.5.3. Applications .................................. 25 2.6. ScanningIonMassSpectroscopy(SIMS) .................. 27 2.6.1. Fundamentals ................................. 27 2.6.2. Equipment ................................... 27 2.6.3. Applications .................................. 29 2.7. ElectronSpectroscopyChemicalAnalysis(ESCA) ........... 29 2.7.1. Fundamentals ................................ 29 2.7.2. Equipment ................................... 31 2.7.3. Applications ................................ 31 . 2.8. InfraredSpectroscopy(IR)forSurfaceAnalysis ............. 31 2.8.1. Fundamentals ................................ 31 2.8.2. Equipment .................................... 40 2.8.3. Applications ................................. 40 2.9. SurfaceEnergyandContactAngleMeasurement ............ 42 2.9.1. Fundamentals ................................ 42 2.9.2. Equipment ................................... 44 2.9.3. Applications ................................. 44 3. BulkAnalysis 3.1. AtomicSpectroscopy(AS) ............................. 45 3.1.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . 45 3.1.2. Equipment .................................. 49 3.1.3. Applications ................................ 49 3.2. InfraredSpectroscopy(IR)forBulkAnalysis ............... 49 3.2.1. Fundamentals ................................. 49 3.2.2. Equipment .................................. 51 3.3. X-RayDiffraction(XRD) .............................. 58 3.3.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 3.3.2. Equipment .................................. 63 3.3.3. Applications ................................. 63 3.4. GelPermeation(GPC),High-pressureLiquid(HPLC),and GasChromatography(GC) ............................ 65 3.4.1. Fundamentals ................................ 65 3.4.2. Equipment ................................. 66 3.4.3. Applications .................................. 66 3.5. NuclearMagnetic ResonanceSpectroscopy(NMR)........... 70 3.5.1. Fundamentals ................................ 70 3.5.2. Equipment ................................... 77 3.5.3. Applications ................................ 77 3.6. ThermalAnalysis .................................. 77 Contents ix 3.6.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . 77 3.6.2. Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.6.3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . 79 3.7. ViscometricAnalysis . . . . . . . . . . . . . . . . . . . . . . . . 85 3.7.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . 85 3.7.2. Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . 88 3.7.3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . 88 3.8. X-RayMicroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 89 3.8.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . 89 3.8.2. Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . 90 3.8.3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . 91 3.9. Mass Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 92 3.9.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . 92 3.9.2. Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . 92 3.9.3. Applications . . . . . . . . . . . . . . . . . . . . . . . . . 92 3.10.Ultraviolet Spectroscopy . . . . . . . . . . . . . . . . . . . . . . 92 3.10.1. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . 92 3.10.2. Equipment . . . . . . . . . . . . . . . . . . . . . . . . . 96 3.10.3. Applications . . . . . . . . . . . . . . . . . . . . . . . . 96 4. PaintFormulations 4.1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 4.1.1. ThePaintFormula . . . . . . . . . . . . . . . . . . . . . . 97 4.1.2. Functions ofPaintandCoatings . . . . . . . . . . . . . . . 98 4.1.3. Classification . . . . . . . . . . . . . . . . . . . . . . . . 98 4.2. SolventSystems . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 4.3. WaterborneSystems . . . . . . . . . . . . . . . . . . . . . . . . . 101 4.4. PowderSystems . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 4.5. Electrodeposition Systems . . . . . . . . . . . . . . . . . . . . . 101 4.5.1. AnionicElectrodeposition Coatings . . . . . . . . . . . . . 102 4.5.2. Cationic Electrodeposition Coatings . . . . . . . . . . . . 103 4.6. Thermal SprayPowderCoatings . . . . . . . . . . . . . . . . . . 104 4.7. PlasmaSprayCoatings . . . . . . . . . . . . . . . . . . . . . . . 105 4.7.1. PrinciplesofOperation . . . . . . . . . . . . . . . . . . . 105 4.7.2. PlasmaSprayableThermoplasticPolymers . . . . . . . . . 106 4.7.3. AdvantagesofPlasmaSprayedCoatings . . . . . . . . . . 106 4.8. Fluidized BedCoatings . . . . . . . . . . . . . . . . . . . . . . . 106 4.9. VaporDeposition Coatings . . . . . . . . . . . . . . . . . . . . . 106 4.10. PlasmaPolymerized Coatings . . . . . . . . . . . . . . . . . . . 106
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