Selected Applications of Modern FT-IR Techniques Selected Applications of Modem FT-IR Techniques Koichi Nishikida Perkin-Elmer Corporation Etsuo Nishio Nicolet Japan Corporation Robert W. Hannah Perkin-Elmer Corporation 0 CRC Press cflJ Taylor&FrancisGroup BocaRaton London NewYork CRCPressisanimprintofthe Taylor&FrancisGroup,aninformabusiness CRCPress Taylor&FrancisGroup 6000BrokenSoundParkwayNW,Suite300 BocaRaton,FL33487-2742 ©1995byTaylor&FrancisGroup,LLC eRePressisanimprintofTaylor&FrancisGroup,anInformabusiness NoclaimtooriginalU.S.Governmentworks Thisbookcontainsinformationobtainedfromauthenticandhighlyregardedsources.Reasonableeffortshavebeenmadeto publishreliabledataandinformation,buttheauthorandpublishercannotassumeresponsibilityforthevalidityofallmaterials ortheconsequencesoftheiruse.Theauthorsandpublishershaveattemptedtotracethecopyrightholdersofallmaterialrepro ducedinthispublicationandapologizetocopyrightholdersifpermissiontopublishinthisformhasnotbeenobtained.Ifany copyrightmaterialhasnotbeenacknowledgedpleasewriteandletusknowsowemayrectifyinanyfuturereprint. ExceptaspermittedunderU.S.CopyrightLaw,nopartofthisbookmaybereprinted,reproduced,transmitted,orutilizedinany formbyanyelectronic,mechanical,orothermeans,nowknownorhereafterinvented,includingphotocopying,microfilming, andrecording,orinanyinformationstorageorretrievalsystem,withoutwrittenpermissionfromthepublishers. Forpermissiontophotocopyorusematerialelectronicallyfromthiswork,pleaseaccesswww.copyright.com(http://www.copy right.com!)orcontacttheCopyrightClearanceCenter, Inc.(Ccq,222RosewoodDrive,Danvers,MA01923,978-750-8400. CCCisanot-for-profitorganizationthatprovideslicensesandregistrationforavarietyofusers.Fororganizationsthathavebeen grantedaphotocopylicensebytheCCC,aseparatesystemofpaymenthasbeenarranged. TrademarkNotice:Productorcorporatenamesmaybetrademarksorregisteredtrademarks,andareusedonlyforidentifica tionandexplanationwithoutintenttoinfringe. VisittheTaylor&FrancisWebsiteat http://www.taylorandfrancis.com andtheCRCPressWebsiteat http://www.crcpress.com Contents Preface Xl Part I. Fundamentals 1. Fourier Transform Infrared (FT-IR) System 3 1.1 Principle ofthe FT-IR Spectrometer 3 1.2 Scan Conditions 10 1.2.1 Resolution 10 1.2.2 Detector 11 1.2.3 Apodization 13 1.2.4 Phasecorrection and magnitude spectra 17 Notes and References 17 2. Features and Operation Techniques ofthe Infrared Accessories 19 2.1 Infrared Microscope 19 2.1.1 Principle 19 2.1.2 Experimentalprocedure 21 2.1.3 Features ofIRmicrospectroscopy 22 2.2 AttenuatedTotalReflection (ATR), or MultipleInternal Reflection (MIR) Accessory 26 2.2.1 Principle 26 2.2.2 ATR accessories 28 2.2.3 Experimentalprocedure 31 2.2.4 Features of ATRspectra 32 2.3 Diffuse Reflection Accessory 38 2.3.1 Principle 38 2.3.2 Experimentalprocedure 39 2.3.3 Featuresofdiffusereflection spectra 39 2.4 Photo-AcousticDetector 42 2.4.1 Principle 42 2.4.2 Experimentalprocedure 44 2.4.3 Features ofthe PA-FTIR method 45 v vi Contents 2.5 Fixed Angle and Variable Angle Specular Reflection Accessories 46 2.5.1 Principle 46 2.5.2 Specularreflection accessory 48 2.5.3 Experimentalprocedure 49 2.5.4 Features of specularreflection spectroscopy 49 2.6 EmissionAccessory 54 2.6.1 Principle 54 2.6.2 Emission accessory 55 2.6.3 Experimentalprocedure 55 2.6.4 Features ofemissionspectroscopy 56 Notes and References 57 Part II. Selected Applications of FT-IR Spectroscopy 3. Analysis of Film and Film-like Samples 61 3.1 DichroicMeasurements ofDrawnPolymer Films 61 3.1A Presentations ofdichroicdata 63 3.1B Dichroicspectraofpoly(ethylene) 65 3.1C Orientation ofdrawn poly(propylene)film (I) - Transmission 68 3.1D Orientation ofdrawn poly(propylene)film (II) - ATR 71 3.2 Analysis of Foreign Matterin Polymers 74 3.2A Thinfilm formed on polymerplate - KBr pellet (Johnson method) 74 3.2B Foreignmatterdeposit on poly(imide) multilayerprintedcircuit board - KBr pellet 76 3.2C Fisheye ofpoly(ethylene)film - Microscope 78 3.2D Foreignmatterin polymerfilm (I)--Microscope 80 3.2E Foreign matterin polymerfilm (II) --Microscope 82 3.3 Layer Structures, Surface Treatments and ChemicalChanges in Polymer Films 84 3.3A Structure of eight-layerlaminatefilm-- Microscope 84 3.3B Layer structure of automobile paint-- Microscope 86 3.3C Photochemicalreaction ofpolymer(I)-- Microscope 88 3.3D Photochemicalreaction of polymer(II) - PAS 90 3.3E Pigment ofglass-reinforced plastic-- Microscope 92 3.3F ObtainingIR spectraof surface coating--ATR 94 3.4 Analysis ofVideo Tapes, Tires, and Black Samples 96 3.4A IRspectraoftires (I) --Transmission, 96 3.4B IR spectraoftires (II) - ATR 98 3.4C Layer structure ofvideo tape (I) - ATR 100 3.4D Layer structure ofvideo tape (II) - PAS 102 Contents vii 3.5 Analysis ofPrinted Substances 104 3.5A Peelingof prints(I) - ATR 104 3.5B Peelingof prints (II) - ATR 106 4. Analysis of Fibers and Clothes 109 4A Observationofsilane couplingreagentbondedto surfaceof glass fiber (I) - Transmission 110 4B Observationof silane couplingreagentbondedto surface ofglass fiber (II) - KBr pellet 112 4C Infrared dichroism of Kevlarfiber (I) - Microscope 114 4D Infrared dichroism of Kevlar fiber (II) - PAS 116 4E Surface treatment offiber - ATR 118 4F Hair treatment reagent- Micro-ATR 120 5. Powder and Bulky Samples 123 5.1 Diffuse Reflection 123 5.lA Diffusereflection ofsilica (I) - Particlesize 126 5.1B Diffusereflection ofsilica (II) - Dilutioneffect 128 5.1C IRspectraof adsorbent ofcatalyst- Diffusereflection 130 5.1D Silanolband ofsilica gel- Diffusereflection 132 5.1E Spot of thin layer chromatograph- Diffuse reflection 134 5.lF Analysis ofliquid chromatographyeffluent-- Diffuse reflection 136 5.1G Analysis of photocopiertoner- Diffuse reflection 138 5.1H Quantitative analysis - Kubelka-Munkcorrection 140 5.2 Photoacoustic-FTIR(PA-FTIR)Technique 142 5.2A Surfacecoatingof silicagel- PAS 142 5.2B Surfacecoatingof powderdetergent- PAS 145 6. Thin Films Formed on Solid Surfaces 147 6.1 Laminate Films on Metal Plates 147 6.1A Laminatefilm on the inner surface of aluminumcan (I)- Specularreflection 147 6.1B Laminatefilm on the inner surfaceof aluminumcan (II)- ATR 149 6.2 Langmuir-Blodgett(LB) Films 151 6.2A LBfilm on metal plate(I)- Grazingangle IR-RAS 151 6.2B LBfilm on metalplate(II)- Grazingangle IR-RAS 153 6.2C LBfilm on CaF plate - Transmission 156 2 6.2D LBfilm formed on silica plate (I) - External reflection 158 6.2E LBfilm formed on silica plate (II) - External reflection 160 6.2F LBfilm formed on silica plate (III) - Externalreflection 162 viii Contents 6.3 Thin Oxide Layers Formed on MetalSurfaces 165 6.3A Barrier type oxide on aluminum(I) - Grazing angle IR-RAS with KK analysis 165 6.3B Barrier type oxide on aluminum(II) -- Emission 167 6.3C Barrier type oxide on aluminum(III) - ATRmethod 170 6.3D Lubricant oflow-density hard disk media - IR-RAS 172 6.3E Lubricant of high-density hard disk media (I)- Grazing angle IR-RAS 174 6.3F Lubricant ofhigh-density harddisk media (II) - Grazing angle IR-RAS 176 7. Liquid Samples 179 7A Association ofglycinoligomer - ATR 179 7B Association ofsurfactantin water -- ATR 182 7C Difference spectroscopy and molecular interaction 185 7D Interactionbetween polymer and organic acidin solution- Transmission 188 7E Analysisof milk- ATR 190 8. Biological Samples 193 8A IR spectraof bacteria--Transmission 193 8B Denaturation of protein-- Diffuse reflection 196 8C Structurechange bydrawing SCMK--Transmission 199 8D Pigment ofbutterflywing--Diffuse reflection 202 9. Analysis of Semiconducting and Superconducting Materials 205 9.1 IR Spectraof Siand GaAs Wafers .205 9.lA Absorption and reflection spectra of Siwafer(I) 206 9.1B Absorption and reflection spectra of Siwafer (II) 208 9.1C Removal ofinterference fringe pattern (I) 211 9.lD Removal ofinterference fringe pattern (II) 214 9.1E Impuritiesin Siwafer--Transmission 216 '9.1F SrOz layer on surface of Si wafer(I)- ATR 218 9.lG SiOzlayer on surface of Siwafer(II) - ATR 220 9.2 IR Spectrum ofa Superconductive Material 222 9.2A Microspectroscopy ofa super-conductive material--Microscope 222 Contents ix 10. HyphenatedTechniques 225 10.1 LC-FTIRTechniques 225 10.lA GPC-FTIR analysis ofpoly(ethylene) additives 226 10.lB Characterization ofpoly(propylene)by GPC-FTIR 229 10.lC Characterizationofpoly(ethylene) by GPC-FTIR 232 10.2 GC-FTIRTechnique 234 1O.2A PyrolysisGC-FTIRanalysisofsilanecouplingreagent ofglassfiber 235 10.2B Supercriticalfluid extraction GC-FTIRanalysis of Basil 237 10.3 TG-IRTechnique 240 1O.3A Thermaldecompositionstudy ofaspertame 242 1O.3B Thermaldecomposition of poly(vinylchloride) 244 11. Application ofData HandlingSoftware 247· 11.1 Deconvolution 247 11.1A Smoothingand difference spectroscopymethod(Hannahmethod) 248 1UB Fourierdeconvolutiontechnique 250 11.2 Derivative Spectra 252 11.2A Fine structure analysisby derivative spectroscopy 253 11.2B Study ofisomer using derivative spectroscopy 256 11.3 Simulationwith Curve-Fitting 258 1104 Kramers-Kronig Analysis 260 11AA Assignment of plastics 260 11.4B Surface coatingof organic lens 262 11AC Absorptionspectrumofintractablesample (I3-SiC) 264 11.5 Chemometrics 266 11.5A Determinationofgasoline octane number 267 11.5B Groupingand trend analysis byfactor analysis 270 11.5C Obtainingpure spectrafrom mixture 272 A Diagramto ClassifyPolymers by IR Spectra 275 Index 277