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Molecular Dynamics of Polymers at Nanometric Length Scales: From Thin Layers to Isolated Coils

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Recent Advances in Broadband Dielectric Spectroscopy

Abstract

The (dynamic) glass transition of polymers in nanometer thin layers is both a prevailing but as well a highly controversial topic. In the current review the literature for the most studied case of polystyrene (as freestanding films or as deposited and suspended layers) will be discussed. Based on this, the extraordinary impact of sample preparation is immediately evident and outlined in detail. Recent results are presented on nanometric thin (≥5 nm) layers of polystyrene (PS) having widely varying molecular weights and polymethylmethacrylate (PMMA) deposited on different substrates. For the dielectric measurements two sample geometries are employed: the conventional technique using evaporated electrodes and a recently developed approach taking advantage of silica nanostructures as spacers. All applied methods deliver the concurring result that deviations from glassy dynamics and from the glass transition of the bulk never exceed margins of ±3 K independent of the layer thickness, the molecular weight of the polymer under study and the underlying substrate. Novel experiments are described on thin layers of polyisoprene, a type A polymer, having relaxation processes on two different length scales, the segmental and the normal mode. A further exciting perspective is the measurement of the dynamics of isolated polymer coils, for which first results will be presented.

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References

  1. Keddie J, Jones R, Cory R (1994) Size-dependent depression of the glass transition temperature in polymer films. Europhys Lett 27:59

    Article  ADS  Google Scholar 

  2. Xie F, Zhang HF, Lee FK, Du B, Tsui OKC (2002) Effect of low surface energy chain ends on the glass transition temperature of polymer thin films. Macromolecules 35:1491–1492

    Article  ADS  Google Scholar 

  3. Forrest JA, Dalnoki-Veress K, Stevens JR, Dutcher JR (1996) Effect of free surfaces on the glass transition temperature of thin polymer films. Phys Rev Lett 77:2002

    Article  ADS  Google Scholar 

  4. DeMaggio G, Frieze W, Gidley D, Zhu M, Hristov HA, Yee AF (1997) Interface and surface effects on the glass transition in thin polystyrene films. Phys Rev Lett 78:1524

    Article  ADS  Google Scholar 

  5. Forrest JA, Dalnoki-Veress K, Dutcher JR (1997) Interface and chain confinement effects on the glass transition temperature of thin polymer films. Phys Rev E 56:5705

    Article  ADS  Google Scholar 

  6. Jean YC, Zhang R, Cao H, Yuan J-P, Huang C-M, Nielsen B, Asoka-Kumar P (1997) Glass transition of polystyrene near the surface studied by slow-positron-annihilation spectroscopy. Phys Rev B 56:R8459–R8462

    Article  ADS  Google Scholar 

  7. Fukao K, Miyamoto Y (1999) Glass transition temperature and dynamics of α-process in thin polymer films. Europhys Lett 46:649

    Article  ADS  Google Scholar 

  8. Forrest JA, Mattsson J (2000) Reductions of the glass transition temperature in thin polymer films: probing the length scale of cooperative dynamics. Phys Rev E 61:R53–R56

    Article  ADS  Google Scholar 

  9. Fryer D, Nealey P, Pablo J (2000) Thermal probe measurements of the glass transition temperature for ultrathin polymer films as a function of thickness. Macromolecules 33:6439

    Article  ADS  Google Scholar 

  10. Fukao K, Miyamoto Y (2000) Glass transitions and dynamics in thin polymer films: dielectric relaxation of thin films of polystyrene. Phys Rev E 61:1743

    Article  ADS  Google Scholar 

  11. Ge S, Pu Y, Zhang W, Rafailovich M, Sokolov J (2000) Shear modulation force microscopy study of near surface glass transition temperatures. Phys Rev Lett 85:2340

    Article  ADS  Google Scholar 

  12. Mattson J, Forrest J, Börjesson L (2000) Quantifying glass transition behavior in ultrathin free-standing polymer films. Phys Rev E 62:5187

    Article  ADS  Google Scholar 

  13. Zhao J-H, Kiene M, Hu C, Ho PS (2000) Thermal stress and glass transition of ultrathin polystyrene films. Appl Phys Lett 77:2843–2845

    Article  ADS  Google Scholar 

  14. Dalnoki-Veress K, Forrest J, Murray C, Gigault C, Dutcher J (2001) Molecular weight dependence of reductions in the glass transition temperature of thin, freely standing polymer films. Phys Rev E 63:031801

    Article  ADS  Google Scholar 

  15. Fryer DS, Peters RD, Kim EJ, Tomaszewski JE, de Pablo JJ, Nealey PF, White CC, Wu W-l (2001) Dependence of the glass transition temperature of polymer films on interfacial energy and thickness. Macromolecules 34:5627–5634

    Article  ADS  Google Scholar 

  16. Fukao K, Miyamoto Y (2001) Slow dynamics near glass transitions in thin polymer films. Phys Rev E 64:011803

    Article  ADS  Google Scholar 

  17. Kawana S, Jones R (2001) Character of the glass transition in thin supported polymer films. Phys Rev E 63:021501

    Article  ADS  Google Scholar 

  18. Tate RS, Fryer DS, Pasqualini S, Montague MF, de Pablo JJ, Nealey PF (2001) Extraordinary elevation of the glass transition temperature of thin polymer films grafted to silicon oxide substrates. J Chem Phys 115:9982–9990

    Article  ADS  Google Scholar 

  19. Tsui OKC, Russell TP, Hawker CJ (2001) Effect of interfacial interactions on the glass transition of polymer thin films. Macromolecules 34:5535–5539

    Article  ADS  Google Scholar 

  20. Tsui OKC, Zhang HF (2001) Effects of chain ends and chain entanglement on the glass transition temperature of polymer thin films. Macromolecules 34:9139–9142

    Article  ADS  Google Scholar 

  21. Ellison CJ, Torkelson JM (2002) Sensing the glass transition in thin and ultrathin polymer films via fluorescence probes and labels. J Polym Sci, Part B: Polym Phys 40:2745–2758

    Article  ADS  Google Scholar 

  22. Ellison C, Kim S, Hall D, Torkelson J (2002) Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: novel fluorescence measurements. Eur Phys J E 8:155

    Article  Google Scholar 

  23. Fukao K, Uno S, Miyamoto Y, Hoshino A, Miyaji H (2002) Relaxation dynamics in thin supported polymer films. J Non-Cryst Solids 307–310:517–523

    Article  Google Scholar 

  24. Ellison C, Torkelson J (2003) The distribution of glass-transition temperatures in nanoscopically confined glass formers. Nat Mater 2:695

    Article  ADS  Google Scholar 

  25. Efremov M, Olson E, Zhang M, Zhang Z, Allen L (2003) Glass transition in ultrathin polymer films: calorimetric study. Phys Rev Lett 91:085703

    Article  ADS  Google Scholar 

  26. Kanaya T, Miyazaki T, Watanabe H, Nishida K, Yamano H, Tasaki S, Bucknall D (2003) Annealing effects on thickness of polystyrene thin films as studied by neutron reflectivity. Polymer 44:3769–3773

    Article  Google Scholar 

  27. Sharp JS, Forrest JA (2003) Free surfaces cause reductions in the glass transition temperature of thin polystyrene films. Phys Rev Lett 91:235701

    Article  ADS  Google Scholar 

  28. D’Amour JN, Okoroanyanwu U, Frank CW (2004) Influence of substrate chemistry on the properties of ultrathin polymer films. Microelectron Eng 73–74:209–217

    Article  Google Scholar 

  29. Ellison CJ, Ruszkowski RL, Fredin NJ, Torkelson JM (2004) Dramatic reduction of the effect of nanoconfinement on the glass transition of polymer films via addition of small-molecule diluent. Phys Rev Lett 92:095702

    Article  ADS  Google Scholar 

  30. Efremov M, Olson E, Zhang M, Zhang Z, Allen L (2004) Probing glass transition of ultrathin polymer films at a time scale of seconds using fast differential scanning calorimetry. Macromolecules 37:4607

    Article  ADS  Google Scholar 

  31. Fakhraai Z, Sharp JS, Forrest JA (2004) Effect of sample preparation on the glass-transition of thin polystyrene films. J Polym Sci, Part B: Polym Phys 42:4503–4507

    Article  ADS  Google Scholar 

  32. Miyazaki T, Nishida K, Kanaya T (2004) Thermal expansion behavior of ultrathin polymer films supported on silicon substrate. Phys Rev E 69:061803

    Article  ADS  Google Scholar 

  33. Singh L, Ludovice PJ, Henderson CL (2004) Influence of molecular weight and film thickness on the glass transition temperature and coefficient of thermal expansion of supported ultrathin polymer films. Thin Solid Films 449:231–241

    Article  ADS  Google Scholar 

  34. Ellison CJ, Mundra MK, Torkelson JM (2005) Impacts of polystyrene molecular weight and modification to the repeat unit structure on the glass transition-nanoconfinement effect and the cooperativity length scale. Macromolecules 38:1767–1778

    Article  ADS  Google Scholar 

  35. Fakhraai Z, Forrest J (2005) Probing slow dynamics in supported thin polymer films. Phys Rev Lett 95:025701

    Article  ADS  Google Scholar 

  36. Lupaşcu V, Huth H, Schick C, Wübbenhorst M (2005) Specific heat and dielectric relaxations in ultra-thin polystyrene layers. Thermochim Acta 432:222

    Article  Google Scholar 

  37. Huth H, Minakov A, Schick C (2006) Differential AC-chip calorimeter for glass transition measurements in ultrathin films. J Polym Sci, Part B: Polym Phys 44:2996

    Article  ADS  Google Scholar 

  38. Inoue R, Kanaya T, Miyazaki T, Nishida K, Tsukushi I, Shibata K (2006) Glass transition and thermal expansivity of polystyrene thin films. Mater Sci Eng A 442:367

    Article  Google Scholar 

  39. Koh Y, McKenna G, Simon S (2006) Calorimetric glass transition temperature and absolute heat capacity of polystyrene ultrathin films. J Polym Sci, Part B: Polym Phys 44:3518

    Article  ADS  Google Scholar 

  40. Lupaşcu V, Picken SJ, Wübbenhorst M (2006) Cooperative and non-cooperative dynamics in ultra-thin films of polystyrene studied by dielectric spectroscopy and capacitive dilatometry. J Non-Cryst Solids 352:5594–5600

    Article  ADS  Google Scholar 

  41. Mundra MK, Ellison CJ, Behling RE, Torkelson JM (2006) Confinement, composition, and spin-coating effects on the glass transition and stress relaxation of thin films of polystyrene and styrene-containing random copolymers: sensing by intrinsic fluorescence. Polymer 47:7747–7759

    Article  Google Scholar 

  42. O’Connell P, McKenna G (2006) Dramatic stiffening of ultrathin polymer films in the rubbery regime. Eur Phys J E 20:143–150

    Article  Google Scholar 

  43. Akabori K-I, Tanaka K, Takahara A, Kajiyama T, Nagamura T (2007) Substrate effect on mechanical relaxation of polystyrene in ultrathin films. Eur Phys J Spec Top 141:173–180

    Article  Google Scholar 

  44. Bodiguel H, Fretigny C (2007) Viscoelastic properties of ultrathin polystyrene films. Macromolecules 40:7291–7298

    Article  ADS  Google Scholar 

  45. Cheng W, Sainidou R, Burgardt P, Stefanou N, Kiyanova A, Efremov M, Fytas G, Nealey P (2007) Elastic properties and glass transition of supported polymer thin films. Macromolecules 40:7283

    Article  ADS  Google Scholar 

  46. Huth H, Minakov A, Serghei A, Kremer F, Schick C (2007) Differential AC-chip calorimeter for glass transition measurements in ultra thin polymeric films. Eur Phys J Spec Top 141:153

    Article  Google Scholar 

  47. Miyazaki T, Inoue R, Nishida K, Kanaya T (2007) X-ray reflectivity studies on glass transition of free standing polystyrene thin films. Eur Phys J Spec Top 141:203–206

    Article  Google Scholar 

  48. Mundra M, Ellison C, Rittigstein P, Torkelson J (2007) Fluorescence studies of confinement in polymer films and nanocomposites: glass transition temperature, plasticizer effects, and sensitivity to stress relaxation and local polarity. Eur Phys J Spec Top 141:143

    Article  Google Scholar 

  49. Napolitano S, Wübbenhorst M (2007) Dielectric signature of a dead layer in ultrathin films of a nonpolar polymer. J Phys Chem 111:9197

    Article  Google Scholar 

  50. Priestley R, Broadbelt L, Torkelson J, Fukao K (2007) Glass transition and α-relaxation dynamics of thin films of labeled polystyrene. Phys Rev E 75:061806

    Article  ADS  Google Scholar 

  51. Svanberg C (2007) Glass transition relaxations in thin suspended polymer films. Macromolecules 40:312–315

    Article  ADS  Google Scholar 

  52. Kim S, Roth C, Torkelson J (2008) Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: novel, self-referencing fluorescence method. J Polym Sci, Part B: Polym Phys 46:2754

    Article  ADS  Google Scholar 

  53. Koh YP, Simon SL (2008) Structural relaxation of stacked ultrathin polystyrene films. J Polym Sci, Part B: Polym Phys 46:2741–2753

    Article  ADS  Google Scholar 

  54. O’Connell PA, Hutcheson SA, McKenna GB (2008) Creep behavior of ultra-thin polymer films. J Polym Sci, Part B: Polym Phys 46:1952–1965

    Article  ADS  Google Scholar 

  55. Raegen A, Massa M, Forrest J, Dalnoki-Veress K (2008) Effect of atmosphere on reductions in the glass transition of thin polystyrene Films. Eur Phys J E 27:375

    Article  Google Scholar 

  56. Serghei A, Huth H, Schick C, Kremer F (2008) Glassy dynamics in thin polymer layers having a free upper interface. Macromolecules 41:3636

    Article  ADS  Google Scholar 

  57. Bernazzani P, Sanchez R (2009) Structural and thermal behavior of polystyrene thin films using ATR–FTIR–NanoDSC measurements. J Therm Anal Calorim 96:727

    Article  Google Scholar 

  58. Inoue R, Kanaya T, Nishida K, Tsukushi I, Telling MTF, Gabrys BJ, Tyagi M, Soles C, Wu W-I (2009) Glass transition and molecular mobility in polymer thin films. Phys Rev E 80:031802

    Article  ADS  Google Scholar 

  59. Kanaya T, Inoue R, Kawashima K, Miyazaki T, Tsukushi I, Shibata K, Matsuba G, Nishida K, Hino M (2009) Glassy dynamics and heterogeneity of polymer thin films. J Phys Soc Jpn 78:041004

    Article  ADS  Google Scholar 

  60. Kim S, Hewlett S, Roth C, Torkelson J (2009) Confinement effects on glass transition temperature, transition breadth, and expansivity: comparison of ellipsometry and fluorescence measurements on polystyrene films. Eur Phys J E 30:83

    Article  Google Scholar 

  61. Lu H, Chen W, Russell TP (2009) Relaxation of thin films of polystyrene floating on ionic liquid surface. Macromolecules 42:9111–9117

    Article  ADS  Google Scholar 

  62. Rotella C, Napolitano S, Wübbenhorst M (2009) Segmental mobility and glass transition temperature of freely suspended ultrathin polymer membranes. Macromolecules 42:1415

    Article  ADS  Google Scholar 

  63. Mapesa E, Erber M, Tress M, Eichhorn K-J, Serghei A, Voit B, Kremer F (2010) Glassy dynamics in nanometer thin layers of polystyrene. Eur Phys J Spec Top 189:173

    Article  Google Scholar 

  64. Napolitano S, Wübbenhorst M (2010) Structural relaxation and dynamic fragility of freely standing polymer films. Polymer 51:5309–5312

    Google Scholar 

  65. Rotella C, Napolitano S, Cremer LD, Koeckelberghs G, Wübbenhorst M (2010) Distribution of segmental mobility in ultrathin polymer films. Macromolecules 43:8686–8691

    Article  ADS  Google Scholar 

  66. Tress M, Erber M, Mapesa E, Huth H, Müller J, Serghei A, Schick C, Eichhorn K-J, Voit B, Kremer F (2010) Glassy dynamics and glass transition in nanometric thin layers of polystyrene. Macromolecules 43:9937–9944

    Article  ADS  Google Scholar 

  67. Clough A, Peng D, Yang Z, Tsui OKC (2011) Glass transition temperature of polymer films that slip. Macromolecules 44:1649–1653

    Article  ADS  Google Scholar 

  68. Dinelli F, Ricci A, Sgrilli T, Baschieri P, Pingue P, Puttaswamy M, Kingshott P (2011) Nanoscale viscoelastic behavior of the surface of thick polystyrene films as a function of temperature. Macromolecules 44:987–992

    Article  ADS  Google Scholar 

  69. Fukao K, Terasawa T, Oda Y, Nakamura K, Tahara D (2011) Glass transition dynamics of stacked thin polymer films. Phys Rev E 84:041808

    Article  ADS  Google Scholar 

  70. Glynos E, Frieberg B, Oh H, Liu M, Gidley DW, Green PF (2011) Role of molecular architecture on the vitrification of polymer thin films. Phys Rev Lett 106:128301

    Article  ADS  Google Scholar 

  71. Inoue R, Kawashima K, Matsui K, Kanaya T, Nishida K, Matsuba G, Hino M (2011) Distributions of glass-transition temperature and thermal expansivity in multilayered polystyrene thin films studied by neutron reflectivity. Phys Rev E 83:021801

    Article  ADS  Google Scholar 

  72. Inoue R, Kawashima K, Matsui K, Nakamura M, Nishida K, Kanaya T, Yamada NL (2011) Interfacial properties of polystyrene thin films as revealed by neutron reflectivity. Phys Rev E 84:031802

    Article  ADS  Google Scholar 

  73. Kim S, Torkelson JM (2011) Distribution of glass transition temperatures in free-standing, nanoconfined polystyrene films: a test of de Gennes’ sliding motion mechanism. Macromolecules 44:4546–4553

    Article  ADS  Google Scholar 

  74. Napolitano S, Rotella C, Wübbenhorst M (2011) Is the reduction in tracer diffusivity under nanoscopic confinement related to a frustrated segmental mobility? Macromol Rapid Commun 32:844–848

    Article  Google Scholar 

  75. Napolitano S, Wübbenhorst M (2011) The lifetime of the deviations from bulk behaviour in polymers confined at the nanoscale. Nat Commun 2:260

    Article  Google Scholar 

  76. Paeng K, Swallen SF, Ediger MD (2011) Direct measurement of molecular motion in freestanding polystyrene thin films. J Am Chem Soc 133:8444–8447

    Article  Google Scholar 

  77. Paeng K, Ediger MD (2011) Molecular motion in free-standing thin films of poly(methyl methacrylate), poly(4-tert-butylstyrene), poly(α-methylstyrene), and poly(2-vinylpyridine). Macromolecules 44:7034–7042

    Article  ADS  Google Scholar 

  78. García-Turiel J, Jérôme B (2007) Solvent retention in thin polymer films studied by gas chromatography. Colloid Polym Sci 285:1617–1623

    Article  Google Scholar 

  79. Perlich J, Körstgens V, Metwalli E, Schulz L, Georgii R, Müller-Buschbaum P (2009) Solvent content in thin spin-coated polystyrene homopolymer films. Macromolecules 42:337

    Article  ADS  Google Scholar 

  80. Serghei A, Kremer F (2008) Metastable states of glassy dynamics, possibly mimicking confinement-effects in thin polymer films. Macromol Chem Phys 209:810

    Article  Google Scholar 

  81. Serghei A, Huth H, Schellenberger M, Schick C, Kremer F (2005) Pattern formation in thin polystyrene films induced by an enhanced mobility in ambient air. Phys Rev E 71:061801

    Article  ADS  Google Scholar 

  82. Labahn D, Mix R, Schönhals A (2009) Dielectric relaxation of ultrathin films of supported polysulfone. Phys Rev E 79:011801

    Article  ADS  Google Scholar 

  83. Wübbenhorst M, Murray C, Dutcher J (2003) Dielectric relaxations in ultrathin isotactic PMMA films and PS-PMMA-PS trilayer films. Eur Phys J E 12:S109

    Article  Google Scholar 

  84. Serghei A, Kremer F (2008) Broadband dielectric studies on the interfacial dynamics enabled by use of nanostructured electrodes. Rev Sci Instrum 79:026101

    Article  ADS  Google Scholar 

  85. Serghei A, Tress M, Kremer F (2006) Confinement effects on the relaxation time distribution of the dynamic glass transition in ultrathin polymer films. Macromolecules 39:9385

    Article  ADS  Google Scholar 

  86. Serghei A, Tress M, Kremer F (2009) The glass transition of thin polymer films in relation to the interfacial dynamics. J Chem Phys 131:154904

    Article  ADS  Google Scholar 

  87. Erber M, Tress M, Mapesa E, Serghei A, Eichhorn K-J, Voit B, Kremer F (2010) Glassy dynamics and glass transition in thin polymer layers of PMMA deposited on different substrates. Macromolecules 43:7729

    Article  ADS  Google Scholar 

  88. Kremer F, Huwe A, Arndt M, Behrens P, Schwieger W (1999) How many molecules form a liquid? J Phys Condens Matter 11:A175

    Article  ADS  Google Scholar 

  89. Stockmayer W (1967) Dielectric dispersion in solutions of flexible polymers. Pure Appl Chem 15:539

    Article  Google Scholar 

  90. Bahar I, Erman B, Kremer F, Fischer E (1992) Segmental motions of cis-polyisoprene in the bulk state: interpretation of dielectric relaxation data. Macromolecules 25:816

    Article  ADS  Google Scholar 

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Authors and Affiliations

  1. Institute of Experimental Physics I, University of Leipzig, Linnéstr. 5, 04103, Leipzig, Germany

    F. Kremer, E. U. Mapesa & M. Tress

  2. Max Planck Institute of Microstructure Physics, Weinberg 2, 06120, Halle (Saale), Germany

    M. Reiche

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  1. F. Kremer
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  2. E. U. Mapesa
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  3. M. Tress
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  4. M. Reiche
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Correspondence to F. Kremer .

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  1. , Lab. de Mathématiques et Physique, Université de Perpignan, Avenue Paul Alduy 52, Perpignan, 66860, France

    Yuri P. Kalmykov

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Kremer, F., Mapesa, E.U., Tress, M., Reiche, M. (2013). Molecular Dynamics of Polymers at Nanometric Length Scales: From Thin Layers to Isolated Coils. In: Kalmykov, Y. (eds) Recent Advances in Broadband Dielectric Spectroscopy. NATO Science for Peace and Security Series B: Physics and Biophysics. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-5012-8_12

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