Understanding the organization and reorganization of polymer crystals Citation for published version (APA): Tian, M. (2004). Understanding the organization and reorganization of polymer crystals. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR568704 DOI: 10.6100/IR568704 Document status and date: Published: 01/01/2004 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. 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Proefschrift. – ISBN 90-386-2705-X NUR 913 Trefwoorden: polymeerkristallisatie / polymeerkristallen / morfologie / polyethyleen / annealing / smelten / atomaire krachtmicroscopie; AFM Subject headings: polymer crystallization / polymer crystals / morphology / polyethylene / annealing / melting / atomic force microscopy; AFM Copyright 2004, M. Tian Printed by the University Press Facilities, Eindhoven, the Netherlands This research was financially supported by the Dutch Polymer Institute (DPI; project # 131). An electronic version of this thesis is available on the web site of the Eindhoven University of Technology in PDF-format (http://www.tue.nl/bib). Understanding the Organization and Reorganization of Polymer Crystals PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de Rector Magnificus, prof.dr. R.A. van Santen, voor een commissie aangewezen door het College voor Promoties in het openbaar te verdedigen op maandag 18 oktober 2004 om 16.00 uur door Mingwen Tian geboren te BaYan, HeiLongJiang, China Dit proefschrift is goedgekeurd door de promotoren: prof.dr. P.J. Lemstra en prof.dr. M. Dosière Copromotor: dr. J. Loos To my wife Lijing Xue Contents Chapter 1 Introduction 1.1 The phenomenon of polymer crystallization ......................................................... 1 1.2 The impact of crystallization in polymer system…………………….…………….. 4 1.3 Crystallization Theories …………………………………………………………………. 6 1.3.1 Surface nucleation model................................................................................ 8 1.4 Melting of polymer crystals................................................................................. 12 1.5 Crystallization and melting behavior in solutions ............................................... 14 1.6 Morphological details and outstanding issues of polymer crystals ...…………...16 1.6.1 Current view of Morphology and chain arrangement in poylethylene (PE) crystals ................................................................................................................... 16 1.6.2 Annealing and melting behavior of PE crystals............................................ 17 1.7 Aim and scope of this thesis ................................................................................ 20 1.8 References............................................................................................................ 22 Chapter 2 Experimental, sample preparation and techniques 2.1 Preparation of polyethylene solution-grown crystals .......................................... 25 2.1.1 Materials ....................................................................................................... 25 2.1.2 Preparation of solution-grown polyethylene single crystals......................... 25 2.2 n-alkane decoration.............................................................................................. 29 2.3 Atomic force microscopy (AFM) ........................................................................ 30 2.3.1 Contact mode and intermittent-contact mode............................................... 31 2.3.2 In-situ AFM observation at real temperature................................................ 32 2.3.3 AFM measurements...................................................................................... 32 2.3.3.1 Ex-situ annealing experiments............................................................... 32 2.3.3.2 In-situ annealing measurements at real temperature.............................. 33 2.3.4 Atomic force acoustic microscopy (AFAM) ................................................ 34 2.4 Low voltage scanning electron microscopy (LVSEM) ....................................... 36 2.5 Differential scanning calorimetry (DSC), high performance DSC (HPer- DSC), and scanning thermal microscopy (SThM)................................................................ 38 i i Contents 2.5.1 Conventional and HPer- DSC....................................................................... 38 2.5.2 Scanning thermal microscopy (SThM)......................................................... 38 2.6 Small angle X-ray scattering (SAXS).................................................................. 40 2.7 References............................................................................................................ 41 Chapter 3 Formation of solution-grown PE single crystals 3.1 Introduction.......................................................................................................... 43 3.2 Results and discussions........................................................................................ 43 3.2.1 Nucleation and growth of PE single crystals ................................................ 43 3.2.1.1 Isochronous decoration technique.......................................................... 43 3.2.1.2 Ex-situ observation of nucleation and growth ....................................... 49 3.2.1.3 Pseudo self seeding................................................................................ 55 3.2.2 Morphological description of solution-grown PE single crystals................. 56 3.2.3 Thickness determination of solution-grown PE single crystals.................... 59 3.3 Summary.............................................................................................................. 63 3.4 References............................................................................................................ 64 Chapter 4 Annealing behavior of solution-grown PE single crystals 4.1 Introduction.......................................................................................................... 65 4.2 Results and discussion ......................................................................................... 67 4.2.1 Morphology development of polyethylene single crystals on annealing...... 67 4.2.1.1 Swiss-cheese morphology...................................................................... 67 4.2.1.2 In-situ annealing study at real temperature of seeded single crystals.... 69 4.2.1.3 Annealing of ‘pseudo’ self-seeded single crystals................................. 79 4.2.2 Lamellar doubling of solution-grown single crystals ................................... 86 4.3 Summary.............................................................................................................. 93 4.4 References............................................................................................................ 95 Chapter 5 Melting behavior of solution-grown PE single crystals 5.1 Introduction.......................................................................................................... 97 5.2 Results and discussion ......................................................................................... 98 Contents iii 5.2.1 Melting of individual solution-grown PE single crystals ............................. 98 5.2.1.1 Lozenge-shaped crystals ........................................................................ 98 5.2.1.2 Organization and melting of truncated lozenge-shaped crystals ......... 101 5.2.2 Describing