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Industrial Applications of Fast Scanning DSC: New Opportunities for Studying Polyolefin Crystallization

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Fast Scanning Calorimetry

Abstract

This overview attempts to motivate and address the background of industrial interest in fast scanning thermal analysis methods with some of the most frequently applied methods and protocols being summarized. Although the utilized approaches and protocols are generic with respect to industrial type polymer resins, particular emphasis will be on polypropylene systems. The latter are characterized by relatively low crystallization rates and nucleation density, and hence, experimental fast scanning calorimetric techniques which are available on a (more) routine basis can provide significant added value. Of particular interest is in this case:

  • To reach the isothermal crystallization temperature without any ‘disturbance’ of seed structures which can be present in efficiently nucleated systems during the early stages of crystallization before reaching the isothermal crystallization temperature.

  • To obtain a disordered PP glass by applying cooling rates far above the crystallization rate, thus enabling studies on the crystallization mechanism under controlled conditions even during cold crystallization from low temperature.

The insights provided by these type of approaches have been illustrated, based on examples of nucleated and non-nucleated polypropylenes, as well as a polypropylene/polyethylene blend and polypropylene impact copolymers. Fast scanning calorimetry enables to fully identify crystallization kinetics of the different formulations via the double clock-curve, in which the low-temperature curve is specifically attributed to homogeneous nucleation and mesophase formation whereas the high-temperature side is attributed to heterogeneous crystallization, as illustrated by the dominant effect of nucleating agents. The described results suggest in fact that the influence of heterogeneous nucleation in polypropylene is dominant, in comparison to influences arising from variations in molecular structures. In non-nucleated systems, on the other hand, the influence from molar mass and molar mass distribution on the crystallization process is moderate, compared to the influence of microstructure (tacticity). Since sample preparation provides some limitations with respect to applicability of the method, more recent developments involve the use of ultramicrotomed samples, permitting studies on samples displaying different thermal histories or in confined geometries, thus opening up new applications which are of high relevance for industrial practice.

While polyethylenes fundamentally are more difficult to study by the currently available techniques owing to their exceptionally high crystallization rates, we address a relevant development in this area which in principle enables to study the microstructure of polyethylene copolymers. This is illustrated via a series of resins with identical macroscopic composition, but employing different catalyst systems.

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References

  1. Androsch R, Di Lorenzo ML, Schick C, Wunderlich B (2010) Mesophases in polyethylene, polypropylene and poly(1-butene). Polymer 51:4639

    Article  Google Scholar 

  2. Matsuba G, Kaji K, Nishida K, Kanaya T, Imai M (1999) Conformational change and orientation fluctuations of isotactic polystyrene prior to crystallization. Polym J 31:722

    Article  Google Scholar 

  3. Zhu X, Yan D, Fang YJ (2001) In situ FTIR spectroscopic study of the conformational change of isotactic polypropylene during the crystallization process. Phys Chem B 105:12461

    Article  Google Scholar 

  4. Konishi T, Nishida K, Kanaya T, Kaji K (2005) Effect of isotacticity on formation of mesomorphic phase of isotactic polypropylene. Macromolecules 38:8749

    Article  Google Scholar 

  5. De Rosa C, Auriemma F, Resconi L (2005) Influence of chain microstructure on the crystallization kinetics of metallocene-made isotactic polypropylene. Macromolecules 38:10080

    Article  Google Scholar 

  6. Sanchez IC, Eby RK (1975) Thermodynamics and crystallization of random copolymers. Macromolecules 8(1975)

    Google Scholar 

  7. Auriemma F, de Ballesteros OR, De Rosa C, Corradini P (2000) Structural disorder in the α form of isotactic polypropylene. Macromolecules 33:8764

    Article  Google Scholar 

  8. Auriemma F, De Rosa C (2002) Crystallization of metallocene-made isotactic polypropylene: disordered modifications intermediate between the α and γ forms. Macromolecules 35:9057

    Article  Google Scholar 

  9. De Rosa C, Auriemma F, Perretta C (2004) Structure and properties of elastomeric polypropylene from C2 and C2v-symmetric zirconocenes. The origin of crystallinity and elastic properties in poorly isotactic polypropylene. Macromolecules 37:6843

    Article  Google Scholar 

  10. De Rosa C, Auriemma F, De Lucia G, Resconi L (2005) From stiff plastic ot elastic polypropylene: polymorphic transformations during plastic deformation of metallocene-made isotactic polypropylene. Polymer 46:9461

    Article  Google Scholar 

  11. De Rosa C, Auriemma F (2006) Structural-mechanical phase diagram of isotactic polypropylene. J Am Chem Soc 128:11024

    Article  Google Scholar 

  12. De Santis F, Adamovsky SA, Titomanlio G, Schick C (2006) Scanning nanocalorimetry at high cooling rate of isotactic polypropylene. Macromolecules 39:2562

    Article  Google Scholar 

  13. De Santis F, Adamosvsky S, Titomanlio G, Schick C (2007) Isothermal nanocalorimetry of isotactic polypropylene. Macromolecules 40:9026

    Article  Google Scholar 

  14. Mileva D, Androsch R, Zhuravlev E, Schick C (2009) Critical rate of cooling for suppression of crystallization in random copolymers of propylene with ethylene and 1-butene. Thermochim Acta 492:67

    Article  Google Scholar 

  15. Silvestre C, Cimmino S, Duraccio D, Schick C (2007) Isothermal crystallization of isotactic poly(propylene) studied by superfast calorimetry. Macromol Rapid Comm 28:875

    Article  Google Scholar 

  16. Mileva D, Zia Q, Androsch R, Radusch HJ, Piccarolo S (2009) Mesophase formation in poly(propylene-ran-1-butene) by rapid cooling. Polymer 50:5482

    Article  Google Scholar 

  17. Mileva D, Androsch R, Zhuravlev E, Schick C, Wunderlich B (2011) Formation and reorganization of the mesophase of random copolymers of propylene and 1-butene. Thermochim Acta 52:1107

    Google Scholar 

  18. Mileva D, Androsch R, Zhuravlev E, Schick C (2009) Temperature of melting of the mesophase of isotactic polypropylene. Macromolecules 42:7275

    Article  Google Scholar 

  19. Mileva D, Androsch R, Zhuravlev E, Schick C, Wunderlich B (2012) Homogeneous nucleation and mesophase formation in glassy isotactic polypropylene. Polymer 53:277

    Article  Google Scholar 

  20. Elmoumni A, Winter HH, Waddon AJ (2003) Correlation of material and processing time scales with structure development in isotactic polypropylene crystallization. Macromolecules 36:6453

    Article  Google Scholar 

  21. Housmans JW, Steenbakkers RJA, Roozemond PC, Peters GWM, Meijer HEH (2009) Saturation of pointlike nuclei and the transition to oriented structures in flow-induced crystallization of isotactic polypropylene. Macromolecules 42:5728

    Article  Google Scholar 

  22. Ma Z, Balzano L, Portale G, Peters GWM (2014) Flow-induced crystallization in isotactic polypropylene during and after flow. Polymer 55:6140

    Article  Google Scholar 

  23. Van Erp T, Roozemond PC, Peters GWM (2013) Flow-enhanced crystallization kinetics of iPP during cooling at elevated pressure: characterization, validation and development. Macromol Theor Simul 22:309

    Article  Google Scholar 

  24. Boyer SAE, Robinson P, Ganet P, Melis J-P, Haudin J-M (2012) Crystallization of polypropylene at high cooling rates: microscopic and calorimetric studies. J Appl Polym Sci 125:4219

    Article  Google Scholar 

  25. Androsch R (2008) In situ atomic force microscopy of the mesomorphic-monoclinic phase transition in isotactic polypropylene. Macromolecules 41:533

    Article  Google Scholar 

  26. Konishi T, Nishida K, Kanaya T (2006) Crystallization of isotactic polypropylene from prequenched mesomorphic phase. Macromolecules 39:8035

    Article  Google Scholar 

  27. Wang ZG, Hsiao BS, Srinivas S, Brown GM, Tsou AH, Cheng SZD, Stein RS (2001) Phase transformation in quenched mesomorphic isotactic polypropylene. Polymer 42:7561

    Article  Google Scholar 

  28. Cohen Y, Saraf RF (2001) A direct correlation function for mesomorphic polymers and its application to the `smectic' phase of isotactic polypropylene. Polymer 42:5865

    Article  Google Scholar 

  29. Lezak E, Bartczak Z, Galeski A (2006) Plastic deformation behavior of β-phase isotactic polypropylene in plane-strain compression at room temperature. Polymer 46:8562–9574

    Article  Google Scholar 

  30. Cavallo D, Portale G, Balzano L, Azurri F, Bras W, Peters GWM, Alfonso GC (2010) Real-time WAXD detection of mesophase development during quenching of propene/ethylene copolymers. Macromolecules 43:10208

    Article  Google Scholar 

  31. Azurri DF, Floris R, Alfonso GC, Balzano L, Peters GWM (2010) Continuous cooling curves diagrams of propene/ethylene random copolymers. The role of ethylene counits in mesophase development. Macromolecules 43:2890

    Article  Google Scholar 

  32. Meer DW, Pukánszky B, Vansco GJJ (2002) On the dependency of impact behavior on the crystalline morphology in polypropylene. Macromol Sci B41:1105–1121

    Article  Google Scholar 

  33. Pukánszky B, Mudra I, Staniek P (1997) Relation of crystalline structure and mechanical properties of nucleated polypropylene. J Vinyl Addit Technol 3:53–57

    Article  Google Scholar 

  34. Binsbergen FL (1970) Heterogeneous nucleation in the crystallization of polyolefins, part I: chemical and physical nature of nucleating agents. Polymer 5:253

    Article  Google Scholar 

  35. Lotz B, Wittmann JC (1984) Epitaxy of helical polyolefins: polymer blends and polymer-nucleating agent systems. Macromol Chem 185:2043

    Article  Google Scholar 

  36. Wittmann JC, Lotz B (1990) Epitaxial crystallization of polymers on organic and polymeric substances. Prog Polym Sci 15:909

    Article  Google Scholar 

  37. Menyhárd A, Gahleitner M, Varga J, Bernreitner K, Jääskeläinen P, Øysæd H, Pulánszky B (2009) The influence of nucleus density on optical properties in nucleated iPP. Eur Polym J 45:3138

    Article  Google Scholar 

  38. Alcazar D, Ruan J, Thierry A, Lotz B (2006) Structural matching between the polymeric nucleating agent isotactic PVCH and iPP. Macromolecules 39:2832

    Article  Google Scholar 

  39. Langhe DS, Hiltner A, Baer EJ (2012) Effect of additives, catalyst residues and confining substrates on the fractionated crystallization of polypropylene droplets. J Appl Polym Sci 125:2110

    Article  Google Scholar 

  40. Wo DL, Tanner RI (2010) The impact of blue organic and inorganic pigments on the crystallization and rheological properties of isotactic polypropylene. Rheol Acta 49:75

    Article  Google Scholar 

  41. Varga J, Ehrenstein GW (1999) Beta-modification of isotactic polypropylene. In: Karger-Kocsis J (ed) Polypropylene: an A-Z reference. Kluwer, Dordrecht

    Google Scholar 

  42. Nagarajan K, Levon K, Myerson AS (2000) Nucleating agents in polypropylene. J Therm Anal Calorim 59:497

    Article  Google Scholar 

  43. Fillon B, Lotz B, Thierry A, Wittmann JC (1990) Self-nucleation and enhanced nucleation of polymers. Definition of a convenient calorimetric “efficiency scale” and evaluation of nucleating additives in lsotactic polypropylene (α phase). J Polym Sci B Polym Phys 31:1395

    Article  Google Scholar 

  44. Lotz B (1998) α and β phases of isotactic polypropylene: a case of growth kinetics `phase reentrency' in polymer crystallization. Polymer 39:4561–4567

    Article  Google Scholar 

  45. Androsch R, Monami A, Kucera J (2014) Effect of an alpha-phase nucleating agent on the crystallization kinetics of a propylene/ethylene random copolymer at largely different supercooling. J Cryst Growth 408:91

    Article  Google Scholar 

  46. G.W.M. Peters TU Eindhoven. Private communications

    Google Scholar 

  47. Vanden Poel G, Mathot V (2006) High-speed/high performance differential scanning calorimetry (HPer DSC): temperature calibration in the heating and cooling mode and minimization of thermal lag. Thermochim Acta 446:41

    Article  Google Scholar 

  48. Vanden Poel G, Mathot V (2007) High performance differential scanning calorimetry (HPer DSC): a powerful analytical tool for the study of the metastability of polymers. Thermochim Acta 461:107

    Article  Google Scholar 

  49. Van Herwaarden S, Iervolino E, Van Herwaarden F, Wijffels T, Leenaers A, Mathot V (2011) Design, performance and analysis of thermal lag of the UFS1 twin-calorimeter chip for fast scanning calorimetry using the Mettler Toldeo Flash DSC 1. Thermochim Acta 522:46

    Article  Google Scholar 

  50. Mathot V, Pyda M, Pijpers T, Vanden Poel G, Van de Kerkof E, Van Heerwaarden S, Leenaers A (2011) The Flash DSC 1, a power compensation twin-type, chip-based fast scanning calorimeter (FSC): first findings on polymers. Thermochim Acta 522:36

    Article  Google Scholar 

  51. Vanden Poel G, Istrate D, Magnon A, Mathot V (2012) Performance and calibration of the Flash DSC 1, a new MEMS-based fast scanning calorimeter. J Therm Anal Calorim 110:1533

    Article  Google Scholar 

  52. Schawe JEK (2015) Analysis of non-isothermal crystallization during cooling and reorganization during heating of isotactic polypropylene by fast scanning DSC. Thermochim Acta 603:85–93

    Article  Google Scholar 

  53. Rhoades AM, Williams JL, Androsch R (2015) Crystallization kinetics of polyamide 66 at processing-relevant cooling conditions and high supercooling. Thermochim Acta 603:103

    Article  Google Scholar 

  54. Remerie K, Groenewold J (2012) Morphology formation in polypropylene impact copolymers under static melt conditions: a simulation study. J Appl Polym Sci 125(1):212–223

    Article  Google Scholar 

  55. Cavallo D, Gardella L, Alfonso GC, Mileva D, Androsch R (2012) Effect of comonomer partitioning on the kinetics of mesophase formation in random copolymers of propene and higher alpha-olefins. Polymer 53:4429–4437

    Article  Google Scholar 

  56. Gahleitner M, Wolfschwenger J, Bachner C, Bernreitner K, Neibl W (1996) Crystallinity and mechanical properties of PP-homopolymers as influenced by molecular structure and nucleation. Appl Polym Sci 61:649–657

    Article  Google Scholar 

  57. Müller AJ, Arnal ML (2005) Thermal fractionation of polymers. Prog Pol Sci 39:559

    Article  Google Scholar 

  58. Lorenzo AT, Arnal ML, Müller AJ, Boschiette de Fierro A, Abetz V (2006) High speed SSA thermal fractionation and limitations to the dimensions of lamellar sizes and their distribution. Macromol Chem Phys 207:39

    Article  Google Scholar 

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Acknowledgements

A number of people have contributed in building up and establishing fast scanning calorimetry in our lab. Albert Sargsyan (now DuPont), Geert van den Poel (now DSM engineering Plastics), and Wil van Eijk (DSM Resolve) performed the first experiments on polypropylene formulations and—in particular—contributed to technical advancement of the technique in our lab. Lilian Willems is acknowledged for providing support and contributing experimental results to this study.

In terms of material related aspects we highly appreciate discussions with and continuing interest of a number of colleagues from SABIC STC Geleen, including Marc Herklots, Rieky Steenbakkers (with respect to P.P.) and Mark Boerakker (with respect to P.E.).

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Authors and Affiliations

  1. DSM Resolve, Geleen, The Netherlands

    Daniel Istrate & Ralf Kleppinger

  2. SABIC Technology and Innovation STC-Geleen, Geleen, The Netherlands

    Klaas Remerie

Authors
  1. Daniel Istrate
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  2. Ralf Kleppinger
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  3. Klaas Remerie
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Correspondence to Ralf Kleppinger .

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Editors and Affiliations

  1. Institute of Physics, University of Rostock, Rostock, Germany

    Christoph Schick

  2. SciTe B.V., Katholieke Universiteit Leuven, Geleen, The Netherlands

    Vincent Mathot

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Istrate, D., Kleppinger, R., Remerie, K. (2016). Industrial Applications of Fast Scanning DSC: New Opportunities for Studying Polyolefin Crystallization. In: Schick, C., Mathot, V. (eds) Fast Scanning Calorimetry. Springer, Cham. https://doi.org/10.1007/978-3-319-31329-0_17

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