WrxirepiA Crystallization of polymers Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites.) [) Polymers can crystallize upon cooling from melting, mechanical stretching or solvent evaporation. Crystallization affects optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is estimated by different analytical methods and it typically ranges between 10 and ‘80%, with erystallized polymers often called "semi-crystalline”. The properties of semi-crystalline polymers are determined not only by the degree of erystallinity, but also by the size and orientation of the molecular chains. Contents Crystal mechanisms Solidification from the melt Nucleation Cxystal growth from the melt Crystallization by stretching Crystallization from solution Confined crystallization Degree of crystallinity Kinetics of polymer crystalinity Properties of semicrystalline polymers Thermal and mechanical properties Optical properties See also References Crystallization mechanisms Solidification from the melt wai Coptaaion of seirantCrtazton machine Caton some Whpassevatan comtataton tay Polymers are composed of long molecular chains which form irregular, entangled coils in the melt. Some polymers retain such a disordered structure upon freezing and readily convert into amorphous solids. In other polymers, the chains rearrange upon freezing and form partly ordered regions with a typical size of the order 1 micrometer! Although it would be energetically favorable for the polymer chains to align parallel, such alignment is hindered by the entanglement. Therefore, within the ordered regions, the polymer chains are both aligned and folded. ‘Those regions are therefore neither Gysaline nor amorphous and are classified as semicrystalline. Examples of semi-erysaline polymers AMOPROUS — semicrystaline ave linear polyethylene (PE), polyethylene terephthalate (PET), poytetraluoroethylene (PTFE) or inotacti polypropylene (PP). the arangenent of mec ‘Whether or not polymers can crystallize depends on their molecular structure ~ presence of straight —_somirystline polymers. chains with regularly spaced side groups facilitates erystallization, For example, erystallization occurs ‘much easier in isotactic than in the atactic polypropylene form. Atactic polymers crystallize when the eee HHH Nucleation ‘The stnuctre ofleotacte lyerepyene ‘Nucleation starts with small, nanometer-sized areas where as a result of heat motion some chains or 7” their segments occur parallel. Those seeds can either dissociate, if thermal motion destroys the ‘molecular order, or grow further, ifthe grain size exceeds a certain critical value 415) Apart from the thermal mechanism, nucleation is strongly affected by impurities, dyes, plasticizers, fillers and other additives in the polymer. This is also referred to as heterogeneous nucleation. This effect is poorly understood and irregular, so that the same additive can promote nucleation in one polymer, but not in another. Many of the good nucleating agents are metal salts of organie acids, which themselves are crystalline at the solidification temperature of the polymer solidification.) Th polypropylene Crystal growth from the melt Crystal growth is achieved by the further addition of folded polymer chain segments and only occurs for temperatures below the melting, temperature T,, and above the glass transition temperature Ty. Higher temperatures destroy the molecular arrangement and below the glass transition temperature, the movement of molecular chains is frozen.'*l Nevertheless, secondary crystallization can proceed even below Ty, in the time seale of months and years, This process affects mechanical properties of the polymers and decreases their volume ‘because of a more compact packing of aligned polymer chains.{4l7] olonniccodcrsnnuCrplaioy of soirantCataton nachna aasevatan mate sors Wiss ‘The chains interact via various types of the van der Waals forces, The interaction strength depends on the distance between the parallel chain segments and it determines the mechanical and thermal properties of the polymer..*) ‘The growth of the crystalline regions preferably occurs in the direction of the largest temperature gradient and is suppressed at the top and bottom of the lamellae by the amorphous folded parts at those surfaces. In the case of a strong gradient, the growth has a unidirectional, dendritic character !9! However, if temperature distribution is isotropic and static then lamellae grow radially and form larger quasi-spherical aggregates called spherulites. Spherulites have a size between about 1 and 100 micrometers!) and form a large variety of colored patterns (see, e.g. front images) when observed __Lameliae form during crysialization between crossed polarizers in an optical microscope, which often inelude the "maltese cross" pattern fom the mel. The arow shows the and other polarization phenomena caused by molecular alignment within the individual lamellae of a _aecton of tomporature gradant 1 spherullite.(245) Crystallization by stretching ‘The above mechanism considered crystallization from the melt, which is important for injection ‘molding of plastic components. Another type of crystallization occurs upon extrusion used in making fibers and films. In this process, the polymer is forced through, ¢.g., a nozzle that creates tensile stress which partially aligns its molecules, Such alignment can be considered as crystallization and it affects the material properties, For example the strength of the fiber is greatly increased in the longitudinal direction, and optical properties show large anisotropy along and perpendicular to the fiber axis. Such anisotropy is ‘more enhanced in presence of rod-like fillers such as carbon nanotubes, compared to spherial fillers! Polymer strength i inereased not only by extrusion, but also by blow molding, which is used in the production of plastic tanks and PET bottles.!®! Some polymers which do not crystallize from the melt, ean be partially aligned by stretching.) ‘Schematic model of @ spherulte. Black arrows indicate drecton of molecular alignment ‘Some elastomers which are amorphous in the unstrained state undergo rapid crystallization upon stretching. Crystallization from solution Polymers can also be crystallized from a solution or upon evaporation of a solvent. This process depends on the degree of dilution: in dilute solutions, the molecular chains have no connection with each other and exist as a separate polymer coils in the solution. Inerease in concentration which can occur via solvent evaporation, induces interaction between molecular chains and a possible erystallization as in onlonniccadncrsnnuCrplaioy of soirantCataton nachna wssevatan cmtataton ta the erystallization from the melt.°2] Crystallization from solution may result in the highest degree of polymer crystallinity. For example, highly linear polyethylene can form platelet-like single crystals with a thickness on the order 10-20 nm when crystallized from a dilute solution. The crystal shape can bbe more complex for other polymers, including hollow pyramids, spirals and multilayer dendritic structures 2) Avery different process is precipitation; it uses a solvent which dissolves individual monomers but not the resulting polymer. When a certain degree of polymerization is reached, the polymerized and Stretching direction =} partially crystallized product precipitates out of the solution, The rate of exystallization ean be Tho aranyjomont ofthe melocule ‘monitored by a technique which selectively probes the dissolved fraction, such as nuclear magnetie chains upon erysalizaton by resonanoe.(#1 stretching Confined crystallization ‘When polymers crystallize from an isotropic, bulk of melt or concentrated solution, the crystalline lamellae (10 to 20 nm in thickness) are typically organized into a spherulitic morphology as illustrated above. However, when polymer chains are confined in a space with dimensions of a few tens of nanometers, comparable to or smaller than the lamellar erystal thickness or the radius of gyration, nucleation and growth can be dramatically affected. As an example, when a polymer crystallizes in a confined ultrathin layer, the isotropic spherulitic “organization of lamellar erystals is hampered and confinement ean produce unique lamellar erystal orientations."3! Sometimes the chain alignment is parallel to the layer plane and the erystals are organized as “on-edge” lamellae. In other cases, "in-plane" lamellae with chain orientation perpendicular to the layers are observed. ‘The unique erystal orientation of confined polymers imparts anisotropic properties. In one example the large, in-plane polymer crystals reduce the gas permeability of nanolayered films by almost 2 orders of magnitude.) Degree of crystallinity ‘The fraction of the ordered molecules in polymer is characterized by the degree of erystallinity, which typically ranges between 10% and. £80%.{4) Higher values are only achieved in materials having small molecules, which are usually brittle or in samples stored for long time at temperatures just under the melting point, The latter procedure is costly and is applied only in special eases Most methods of evaluating the degree of crystallinity assume a mixture of perfect erystalline and totally disordered areas; the transition areas are expected to amount to several percent. These methods include density measurement, differential seanning calorimetry (DSC), X- ray diffraction (XRD), infrared spectroscopy and nuclear magnetic resonance (NMR). The measured value depends on the method used, ‘which is therefore quoted together with the degree of erystallinty. 1") olonniccodcrsnnuCrplaioy of soirantCataton nachna “asevatan cmtatnton tay {In addition to the above integral methods, the distribution of crystalline and amorphous regions can be visualized with microscopic techniques, sch as polarized ight mieroseopy and transmission eleetzon mieroseopy Density measurements Chystaline areas are generally more densely packed than amorphous areas. Dear of yan (0%) and danas fea This results in a higher density, up to 15% depending on the material. For (P<) and amorphous (Ps, giem*) polymers. #1 ‘example, polyamide 6 (nylon) has crystalline density p, = 1.24 gicm? and Polymer >D fe |p amorphous desiy p= 1.08 glen), However, moisture which is often present in -yn nas ane Pas sae to Po the sample does affect this type of measurement Polonmethyene(POM) 70-80 164 128 Calorimetry Polyethylene terephthalate (PET) 30-40 | 1.50 | 1.33 ‘Additional energy is released upon melting a semicrystalline polymer. This seat * (een) ‘energy can be measured with differential scanning calorimetry and compared Polybutyiene terephthalate (PBT) 40-60 with that released upon metting ofthe standard sample of the same material with Poheetrafuoroethylene (PTFE) 60-80 | 235 2.00 known crystallization degree. ll Isotacte polypropylene 70-80 | 098 | 0.85 X-ray diffraction sacte pobypropylene oi Regular arrangement of atoms and molecules produce sharp aifraction Peaks ist dens pletylne vom tio boat whereas amorphous regions result in broad halos. The diffraction pattern of polymers usually contains a combination of both. Degree of crystalinity can be Lowensy polyethylene 45-55 | 1.0 | 085 estimated by integrating the relative intensities of the peaks and halos.1 Infrared spectroscopy (IR) Infrared absorption or reflection spectra from crystalline polymers contain additional peaks which are absent in amorphous materials with the same composition, These signals may originate from deformation vibrations of the regular arrangement of molecular chains, From the analysis of these bands, the degree of crystallinity can be estimated.) Nuclear magnetic resonance (NMR) ‘rystaliine and amorphous areas differ by the mobilly of protons. The latter can be monitored through the line shape of NMR signals and used to estimate the degree of crystallinity 9) Kinetics of polymer crystallinity ‘The methods used to determine the degree of exystallinity ean be incorporated over time to measure the kinetics of erystallization. The ‘mast basic model for polymer erystalization kinetics comes from Hoffman nucleation theory. The crystallization process of polymers does not always obey simple chemical rate equations. Polymers can crystallize through a variety of different regimes and unlike simple molecules, the polymer crystal lamellae have two very different surfaces. The two most prominent theories in polymer erystallization kinetics are the Avrami equation and Lauritzen-Hoffman Growth Theory.5! olonniccodcrsnnuCrplaioy of soirantCataton nachna ‘asevatan comtatnton ta Properties of semicrystalline polymers Thermal and mechanical properties ‘Below their glass transition temperature, amorphous polymers are usually hard and brittle because of the low mobility oftheir molecules. Increasing the temperature induces molecular motion resulting in the typical rubber-elastic properties. A constant force applied to a polymer at temperatures above Ty, results in a viscoelastic deformation, ie, the polymer begins to ereep. Heat resistance is usually given for amorphous polymers just below the glass transition temperature."® Relatively strong intermolecular forces in semicrystalline polymers prevent softening even above the glass transition temperature, Their elastic modulus changes significantly only at high (melting) temperature.) It also depends on the degree of crystallinity: higher crystallinity results in a harder and more thermally stable, but also more brittle material, whereas the amorphous regions provide certain elasticity and impact resistance.(*I6! Another characteristic feature of semicrystalline polymers is strong anisotropy of their mechanical properties along the direetion of molecular alignment and perpendicular to it.071 Above the glass transition temperature amorphous chains in a semi-crystalline polymer are ductile and are able to deform plastically. Crystalline regions of the polymer are linked by the amorphous regions. Tie molecules prevent the amorphous and crystalline phases from separating under an applied load. When a tensile stress is applied the semi-crystalline polymer first deforms elastically. While the crystalline regions remain unaffected by the applied stress, the molecular chains of the amorphous phase stretch. Then yielding, which signifies the onset of plastic deformation of the erystalline regions, occurs.) ‘The molecular mechanism for semi-crystalline yielding involves the deformation of crystalline regions of the material via dislocation motion. Dislocations result in coarse oF fine slips in the polymer and lead to erystalline fragmentation and yielding.) Fine slip is defined as a small amount of slip occurring on a large number of planes. Conversely, coarse slip is a large amount of slip on few planes. The yield stress is determined by the creation of dislocations and their resistance to motion.(2°) Alter yielding, a neck is formed in the amorphous region and propagates down the sample length. During necking, the disordered chains align along the tensile direction, forming an ordered structure that demonstrates strengthening due to the molecular reorientation. The flow stress now increases significantly following neck propagation. Mechanical anisotropy increases and the elastic modulus varies along different directions, with a high modulus observed in the draw direction, Drawn semi-crystalline polymers are the strongest polymeric ‘materials due to the stress-induced ordering of the molecular chains.) Other defects, such as voids, oceur in the semi-erystalline polymer under tensile stress and can drive the formation of the neck. The voids ccan be observed via small angle x-ray scattering. Unlike crazes these voids do not transfer stresses.. Notably, cavitation is nat observed under compressive stress or shearing. Evidence Suggests that cavitation also impacts the onset of yielding. The voids are associated with olonniccodcrsnnuCrplaioy of soirantCataton nachna easevatan cmtataton ta the breaking of the amorphous phase. The strength of the crystalline phase determines the importance of cavitation in yielding, If the czystaline structures are weak, they deform easily resulting in yielding. Semi-enstalline polymers with strong crystalline regions resist deformation and cavitation, the formation of voids in the amorphous phase, drives yielding, As done in crystalline materials, particles can be added to semi-crystalline polymers to change the mechanical properties. In crystalline materials the addition of particles works to impede dislocation motion and strengthen the material. However, for many semi-erystalline polymers particle filers weaken the material. Tt has been suggested that for particles to have a toughening effect in polymers the interparticle matrix ligament thickness must be smaller than a certain threshold, Crystalline polymers polypropylene and polyethylene display particle strengthening =) Plastics are viscoelastic materials meaning that under applied stress, their deformation inereases with time (creep). The elastic properties of plasties are therefore distinguished according to the time scale of the testing to short-time behavior (such as tensile test which lasts minutes), shock loading, the behavior under long-term and static loading, as well as the vibration-induced stress.[29! Optical properties Crystalline polymers are usualy opaque because of light scattering on the numerous boundaries between the crystalline and amorphous regions. The density of such boundaries i ower and consequentily, the transparency is higher - either for low (amorphous polymer) ot high (crystalline) degree of erystallinity.(5! For example, atactic polypropylene is usually amorphous and transparent while syndiotactic polypropylene, which has erystalinity ~50%, is opaque!=4) Crystallinity also affects dyeing of polymers: crystalline polymers are more difficult to stain than amorphous ones because the dye molecules penetrate through amorphous regions with greater ease.!*5) See also * Liquid erystal polymer = Modeling of polymer crystals References 1. Andrew Keller (1852). "Morphology of crystallizing polymers’ 2. Charles E. Carraher; Raymond Benedict Seymour (2003 ‘Nature, 169 (4309) 913. doV:10,1038/169913a0 (https:/dol.orgl -Seymour/Carraher's polymer chemistry (ntps:lrbooks.google.co 10.1038%2F 16991320) imv7id=Jg_18B7-4ngC&pg=PA4S&dq=polymer+crystalization*sp herulte#lamellae&c nepage&q=polymeri£20crystalizat ‘on’%20spherulite%20lamellaesi=false). CRC Press. pp. 4345. ISBN 978-0-8247-0806-1 olonniccodcrsnnuCrplaioy of soirantCataton nachna 183. Linda C. Sawyer; David T. Grubb; Gregory F. Meyers (2008). Polymer microsc :Mbooks. google.com/books 7id=T8Kro ‘sds-1gC&pg=PAS). Springer. p. 5. ISBN 978-0-387-72627-4, 4. G. W. Ehrenstain; Richard P. Theriault (2001). Polymeric ‘materials: structure, properties, applications (nti: /Nbooks.googl e.comibooks 7id=_ad2m-bScUC&pqg=PAG7). Hanser Verlag. pp. 67-78. ISBN 878-1-56990-310-0. 5. Georg Menges, Edmund Haberstroh, Walter Michaeli, Ernst ‘Schmachtenbera: Plastics Materials Science (https:!/books goog le.comMbooks?id=R3p4KXOBNAAC&pg=PAG8) Hanser Verlag, 2002, ISBN 3-446-21257-4 6, GW Becker, Ludwig Bottenoruch, Rudolf Binsack, D, Braun: Engineering Thermoplastics. Polyamides. (https//b00ks.google. com/books?id=S3t_ZOMVvQOC&pg=PA340) (in German) Hanser Verlag, 1998 ISBN 3-446- 1648 7. Wilbrand Woebcken, Klaus Stéckhert, HBP Gupta: Plastics Encyclopedia. (in German) Hanser Verlag, 1998, ISBN 3-446- 17968-0 8, Wolfgang Weisbach: Materials science and materials testing (https:/books. google. com/books ?id=dcenroTkKuL gC&pg=PA259) Vieweg * Teubner Verlag, 2007, ISBN 3-8348-0295-6 9, Dendrite (hitps:/farchive.today/20070810172156Mnttp: www. defivfldolmkatlsting.aspx?Action=Quicklink&Search=Dendri& Searchin=Keywords) in the IWF Knowledge and Media gGmbH (Videos and articles on the dendritic crystalization of polypropylene) Patil, N; Balzano, L; Portale, G; Rastogi, S (July 2010). "A Study fon the Chain-Partcle Interaction and Aspect Ratio of Nanoparticles on Structure Development of a Linear Polymer". Macromolecules. 43 (16): 6749-6759. Bibcode:2010MaMol..43.6749P (https//ui.adsabs.harvard.edula s/2010MaMol..43.6749P), doi:10.1021/ma100636V (htips:/do rg/10.10219%2Fma100636v). ISSN 0024-8297 (https:/www.wor Idcat org/issn/0024-9297) 11. Michael Thielen, Klaus Hartwig, Peter Gust: Blow molding of plastic articles (htips://books google.com/books 7id=JNY 1FOuty yeC&pg=PAT3) Hanser Verlag, 2006, ISBN 3-446-22671-0, 10. olonniccodcrsnnuCrplaioy of soirantCataton nachna comtataton ta 42. J. Lehmann (1966). "The observation of the crystallization of high polymer substances from the solution by nuclear magnetic resonance”. Colloid & Polymer Science. 212 (2): 167-168. doi 10.1007/8F01553085 (tips //dol.org/10.1007%2FBFO15530 85). Wang, Haopeng; Jong K. Keum; Anne Hiltner, Eric Baer; Benny Freeman; Artur Rozanski; Andrzej Galeski (6 February 2009), "Confined Crystalization of Polyethylene Oxide in Nanolayer Assemblies". Science. 323 (5915): 757-760. Bibcode:2009Sc)..323..757W (hitps:/ui.adsabs harvard edulab $/2009S6....323..757W). doi 10.1126/science, 1164601 (https:/d oi.org/10.1126%2F science. 1164601), PMID 19197057 (htips:ip bmed nebi.nim.nih,gov/19197057). 14, Gotttied W, Ehrenstein, Gabriela Riedel, Pia Trawiel: Practice of thermal analysis of plastics. (hitps:/books. google.com/book 13, s?id=xythvkmwJxIC&pg=PA148) tlansor Verlag, 2003, [SBN 446-223. 418. Paul. Painter; Michael M. Coleman (1997). "8". Fundamentals of Polymer Science An Introductory Text, Second Edition. CRC Press. Joachim Nentwig: Plastic fms (https:fbooks.google.com/book s?id=sidhvOEdkvoC&pg=PA17) (in German) Hanser Verlag, 2008, ISBN 3-446-40390-6 Martin Bonnet: Plastics in engineering applications: properties, yrocessing and practical use of polymeric materials. (hiips1/b00 ks. google, com/books?id=uGipGKUG3A0C8&pq=PA 149) (in German) Vieweg=Teubner Verlag, 2008 ISBN 3-8348-0349-9 Courtney, T. H. "Mechanical Behavior of Materials”, Waveland Press (2005) , 392-396 Pawlak, A., Galeski A,. Rozanski, A. Cavitation during doformation af semicrystalline polymers, Progress in Polymer Science. (2014) 921-958 Bowden, P., Young, RJ. Deformation Mechanisms in Crystalline Polymers. Journal of Materials Science. (1974), 2034-2051 21, Courtney, T, H.. Mechanical Behavior of Materials, Waveland Press (2005) , 392-396 16, 7 18, 19, 20.sevatan itt of ayn 22. Bartezak, Z., Argon A.S., Weinberg, M. Toughness mechanism 24. Andrew J. Peacock; Alison R. Calhoun (2006). Polymer in semi-crysialline polymer blends. Il. High-density polyethylene chemistry: properties and applications (nitps.lfbooks. google.co toughened with calcium carbonate filer particles. Polymer, 1999. mibooks?id=F PriQJuDE3YC&pg=PA287). Hanser Verlag. 2347-2366. pp. 286-287. ISBN 978-1-56990-397-1 23. James F. Shackelford (2009). Introduction fo Materials Science 25. Agnes Timér-Balazsy: Dinah Eastop (1998). Chemical principles for Enginoors (nttps:llbooks google.com/o00ks7id=STAUVIEXA of fextilo conservation (https:lbooks. google com/b0oks id= Sik (C&pg=PA%68). Prentice Hall. pp. 168-162. ISBN 978-0-13- KVITQGQC&pg=PAI1), Butterworth-Heinemann. p. 11 60126 ISBN 978-0-7506-2620-0. Reveved from ‘htps:ifen wixioeda.orgiwindex op ?ite=Crysalization_of polymersBoldd=894821876" ‘This page was last edited on 8 January 2020, t 09:15 (UTC) ‘ext is avaiable unger tha Creative Commons Attrition Privacy Poy, Wiined ae tonal terms may apply. By using this ste, you agree tothe Terms of U jn, ea non-profit organization olonniccodcrsnnuCrplaioy of soirantCataton nachna ea