Plastics Additives: Advanced Industrial Analysis (Stand Alone)

Modern polymer/additive deformulation is essentially carried out according to three different approaches, in increasing order of sophistication, namely analysis of analytes separated from the polymer (typically an extract), of analytes and polymer in solution, or directly in-polymer (solid state or melt). The current status of conventional, indirect, methods of deformulation of polymer/additive extracts and dissolutions has recently been described in a comprehensive fashion. However, there is an impelling need to tackle polymer/additive deformulations strategically in an ever-increasing order of sophistication in analytical ingenuity, from indirect to direct analysis procedures, from macro to micro, from slow to rapid, from close to remote, from lab to process. This book, containing an outline of the principles and characteristics of relevant instrumental techniques (without unnecessary detail), provides an in-depth overview of various aspects of direct additive analysis by focusing on a wide array of applications in R&D, production, quality control and technical service. The book describes the fundamental characteristics of the arsenal of techniques utilised industrially in direct relation to application in real-life polymer/additive analysis. Instrumental methods are categorized according to general deformulation principles with emphasis on promoting understanding and on effective problem solving. Title page 1 Table of Contents 5 Preface 11 About the Author 13 Acknowledgements 15 In-Polymer Spectroscopic Analysis of Additives 17 Direct Ultraviolet/Visible Spectrophotometry 20 Vapour-phase Ultraviolet Absorption Spectrometry 26 Solid-state Vibrational Spectroscopies 27 Mid-infrared Spectroscopic Analysis 30 Near-infrared Spectroscopy 50 Raman Spectroscopic Techniques 68 Photoacoustic Spectroscopy 82 Emission Spectroscopy 88 Infrared Emission Spectroscopy 88 Molecular Fluorescence Spectroscopy 91 Phosphorescence Spectroscopy 97 Chemiluminescence 98 Nuclear Spectroscopies 110 Solid-state NMR Spectroscopy 111 Nuclear Quadrupole Resonance 126 Electron Spin Resonance Spectroscopy 128 Mössbauer Spectroscopy 136 Dielectric Loss Spectroscopy 139 Ultrasonic Spectroscopy 143 Bibliography 145 General Spectroscopy 145 Direct UV/VIS Spectrophotometry 145 Infrared Spectroscopy 145 Near-infrared Spectroscopy 146 Raman Spectroscopy 146 Photoacoustics 146 Emission Spectroscopy 147 NMR Spectroscopy 147 Electron Spin Resonance Spectroscopy 147 Dielectric Spectroscopy 147 Polymer Characterisation 147 References 148 Polymer/Additive Analysis by Thermal Methods 171 Thermal Analysis Techniques 174 Differential Scanning Calorimetry 179 Differential Thermal Analysis 189 Thermogravimetric Analysis 191 Simultaneous Thermal Analysis Methods 205 (Multi)hyphenated Thermal Analysis Techniques 208 Thermal Microscopy 225 Thermoluminescence 229 Pyrolysis Techniques 230 Pyrolysis–Gas Chromatography 238 Pyrolysis–Mass Spectrometry 251 Pyrolysis–Gas Chromatography–Mass Spectrometry 260 Pyrolysis–Fourier Transform Infrared Spectroscopy 277 Pyrolysis–Gas Chromatography–Fourier Transform Infrared Spectroscopy 279 Pyrolysis–Gas Chromatography–Atomic Emission Detection 280 Temperature-programmed Pyrolysis 282 Thermal Volatilisation and Desorption Techniques 291 Thermal Separation Techniques 294 Direct Solid Sampling Techniques for Gas Chromatography 298 Thermal Desorption–Mass Spectrometric Techniques 315 Bibliography 316 ThermalAnalysis 316 Pyrolysis 317 Thermal Desorption 317 References 317 Lasers in Polymer/Additive Analysis 341 Lasers 341 Laser Ablation 347 Laser Ablation – Plasma Source Spectrometry 351 Laser Spectroscopy 357 Laser-induced Atomic and Molecular Fluorescence Spectrometry 359 Laser-induced Breakdown Spectroscopy 362 Laser Desorption/Ionisation Methods 369 Laser Desorption Mass Spectrometry 370 Laser Ionisation 379 Decoupled Laser Desorption/Ionisation 382 Matrix-assisted Laser Desorption/Ionisation 390 Laser Microprobe Mass Spectrometry 397 Laser Pyrolysis 404 Bibliography 408 Lasers 408 Laser Ablation 408 Laser Spectroscopy/Spectrometry 408 Laser-induced Chemistry 409 Laser Safety 409 References 409 Surface Analytical Techniques for Polymer/Additive Formulations 419 Electron Spectroscopy 424 Auger Electron Spectroscopy 425 X-ray Photoelectron Spectroscopy 427 Surface Mass Spectrometry 436 Secondary Ion Mass Spectrometry 438 Secondary Neutral Mass Spectrometry 455 Ion Scattering Techniques 457 Low-energy Ion Scattering 459 Rutherford Backscattering Spectroscopy 460 Bibliography 462 SurfaceCharacterisation 462 Electron Spectroscopy 463 Surface Mass Spectrometry 463 Ion Scattering Techniques 463 References 463 Microscopy and Microanalysis of Polymer/Additive Formulations 471 Chemical Microanalysis 474 Microscopy and Imaging Techniques 476 Light Microscopy 480 Conventional Optical Microscopy 482 Ultraviolet Microscopy 488 Fluorescence Microscopy 491 Confocal and Laser Microscopy 494 Electron Microscopy 499 Scanning Electron Microscopy 501 Transmission Electron Microscopy 510 Analytical Electron Microscopy 513 Scanning Probe Microscopy Techniques 517 Atomic Force Microscopy 520 Near-field Scanning Optical Microscopy 527 Scanning Kelvin Microscopy 530 Microspectroscopic Imaging of Additives 530 UV/Visible Microspectroscopy 535 Infrared Microspectroscopy and Imaging 537 Laser-Raman Microprobe and Microscopy 548 Fluorescence and Luminescence Imaging 557 Magnetic Resonance Imaging 562 Nuclear Magnetic Resonance Imaging 563 Electron Spin Resonance Imaging 571 X-ray Microscopy and Microspectroscopy 575 X-ray Microradiography 576 Scanning X-ray Microscopy 577 X-ray Microfluorescence 579 Micro X-ray Photoelectron Spectroscopy 580 Ion Imaging of Additives 582 Laser-microprobe Mapping 582 Imaging Secondary Ion Mass Spectrometry 583 Bibliography 589 Light Microscopy 589 Electron Microscopy 589 Scanning Probe Microscopy 590 Near-field Optics 590 Microbeam Analysis 590 Microspectroscopy 591 Imaging/Image Analysis 591 Polymer Microscopy 591 General 592 References 592 Quantitative Analysis of Additives in Polymers 613 Sampling Procedures for Quantitative Analysis of Polymer/Additive Packages 616 Quantitative Analysis of Mineral Filled Engineering Plastics 621 Reverse Engineering of Cured Rubber Compounds 622 Determination of Additive Blends in Polymers 622 Quantitative Solvent and Thermal Extraction 625 Extraction and Quantification of Polyolefin Additives 629 Supercritical Fluid Extraction 630 Quantification of Antioxidants in Polyolefins 631 Determination of Plasticisers by Solvent and Thermal Extraction 635 Oil-extended EPDM 639 Migration Rates of Phthalate Esters from Soft PVC Products 640 Quantitative Chromatographic Methods 640 Quantitative Gas Chromatography 642 Quantitative Liquid Chromatography 644 Quantitative Supercritical Fluid Chromatography 645 Quantitative Thin-layer Chromatography 646 Quantitative Spectroscopic Techniques 649 Quantitative Ultraviolet/Visible Spectrophotometry 653 Quantitative Fluorescence Spectroscopy 655 Quantitative Infrared Spectroscopy 655 Quantitative Near-infrared Spectroscopy 660 Quantitative Raman Spectroscopy 661 Quantitative Nuclear Magnetic Resonance Methods 662 Quantitative Mass Spectrometric Techniques 663 Quantitative Surface Analysis Techniques 667 Quantitative Microscopy 669 Bibliography 670 General Quantitative Analysis 670 Sampling 670 Chromatography 670 Spectroscopy 671 Mass Spectrometry 671 Surface Analysis 671 Chemometric Techniques 671 References 671 Process Analytics 679 In-process Analysers 683 Process Spectroscopy 691 Remote Spectroscopy 693 Process Electronic Spectroscopy 695 Mid-infrared Process Analysis of Polymer Formulations 699 Near-infrared Spectroscopic Process Analysis 709 Process Raman Spectroscopy 717 Process Nuclear Magnetic Resonance 720 Acoustic Emission Technology 732 Real-time Dielectric Spectroscopy 735 Process Chromatography 736 In Situ Elemental Analysis 737 Bibliography 738 Process Analytical Chemistry 738 Process Spectroscopy 738 Process Data Analysis 739 References 739 Modern Analytical Method Development and Validation 747 Status of Existing Methods for Polymer/Additive Analysis 748 In-polymer Additive Analysis: Method Development and Optimisation 748 Certified Reference Materials 752 Analytical Method Validation Approaches 762 Analytical Performance Parameters 767 Interlaboratory Collaborative Studies 771 Validation of Antioxidant Migration Testing 773 Total Validation Process 773 Software/Hardware Validation/Qualification 774 System Suitability 776 Rational Step-by-step Method Development and Validation for Polymer/Additive Analysis 776 Bibliography 778 Method Development and Validation 778 Reference Materials 778 References 778 List of Symbols 783 Acronyms of Techniques 783 Chemical Nomenclature 794 Polymers and Products 794 Additives/Chemicals 796 Physical and Mathematical Symbols 801 Physical and Mathematical Greek Symbols 805 General Abbreviations 806 Subject Index 809 Contains an outline of the principles and characteristics of relevant instrumental techniques, provides an overview of various aspects of direct additive analysis by focusing on an array of applications in R & ;ampD, production, quality control, and technical service.