With a combination of extensional rheology and in-situ small-angle X-ray scattering measurements, the protocol of two-step extension is proposed to investigate the early stage of flow-induced crystallization (FIC) in supercooled isotactic polypropylene melt at 138 °C. After both step strains, the crystallization half-time presents a nonmonotonic dependence on the interval time between two extensional operations, based on which three different stages of structural evolution are defined. In stage I, both nucleation and chain relaxation occur, which enhances the crystallization rate but reduces the final lamellar crystal orientation. In this stage, each part of the melt is considered to have approximately the same dynamics to respond homogeneously to the second extension and thus the system is still dominated by a chain-network. When entering into stage II, the sparse large-scaled crystal is formed to construct a heterogeneous crystal-network superimposed on the chain-network, which decelerates the second extension induced crystallization by causing stress concentration on the crystal-network at low faction. In stage III, the crystal-network dominates the sample deformation due to the formation of abundant lamellar crystal, which recreates the approximately same dynamics for each part of sample and brings about an enhancement of crystallization rate again. The transition from chain- to crystal-network revealed in this work demonstrates a dynamical coupling of chain relaxation, crystal nucleation, and growth in FIC of polymers.
References
1.
Peters
, G. W. M.
, L.
Balzano
, and R. J. A.
Steenbakkers
, “Flow‐induced crystallization
,” in Handbook of Polymer Crystallization
(John Wiley & Sons
, Hoboken, NJ
, 2013
).2.
Peterlin
, A.
, “Drawing and extrusion of semi-crystalline polymers
,” Colloid. Polym. Sci.
265
, 357
–382
(1987
).3.
Keller
, A.
, and J.
Kolnaar
, “Chain extension and orientation: Fundamentals and relevance to processing and products
,” Prog. Colloid Polym. Sci.
92
, 81
–102
(1993
).4.
Wang
, Z.
, Z.
Ma
, and L.
Li
, “Flow-induced crystallization of polymers: Molecular and thermodynamic considerations
,” Macromolecules
49
, 1505
–1517
(2016
).5.
van Meerveld
, J.
, M.
Hütter
, and G. W.
Peters
, “Continuum model for the simulation of fiber spinning, with quiescent and flow-induced crystallization
,” J. Non-Newtonian Fluid Mech.
150
, 177
–195
(2008
).6.
Schultz
, J.
, B. S.
Hsiao
, and J.
Samon
, “Structural development during the early stages of polymer melt spinning by in-situ synchrotron X-ray techniques
,” Polymer
41
, 8887
–8895
(2000
).7.
Janeschitz-Kriegl
, H.
, “How to understand nucleation in crystallizing polymer melts under real processing conditions
,” Colloid. Polym. Sci.
281
, 1157
–1171
(2003
).8.
Chen
, Y.
, D.
Fang
, B. S.
Hsiao
, and Z.
Li
, “Insight into unique deformation behavior of oriented isotactic polypropylene with branched shish-kebabs
,” Polymer
60
, 274
–283
(2015
).9.
Chen
, W.
, X.-Y.
Li
, Y.-P.
Liu
, J.
Li
, W.-M.
Zhou
, L.
Chen
, and L.-B.
Li
, “The spatial correlation between crystalline and amorphous orientations of isotactic polypropylene during plastic deformation: An in situ observation with FTIR imaging
,” Chin. J. Polym. Sci.
33
, 613
–620
(2015
).10.
Graham
, R. S.
, and P. D.
Olmsted
, “Coarse-grained simulations of flow-induced nucleation in semicrystalline polymers
,” Phys. Rev. Lett.
103
, 115702
(2009
).11.
Janeschitz-Kriegl
, H.
, E.
Ratajski
, and M.
Stadlbauer
, “Flow as an effective promotor of nucleation in polymer melts: A quantitative evaluation
,” Rheol. Acta
42
, 355
–364
(2003
).12.
Kumaraswamy
, G.
, A. M.
Issaian
, and J. A.
Kornfield
, “Shear-enhanced crystallization in isotactic polypropylene. 1. Correspondence between in situ rheo-optics and ex situ structure determination
,” Macromolecules
32
, 7537
–7547
(1999
).13.
Graham
, R. S.
, and P. D.
Olmsted
, “Kinetic Monte Carlo simulations of flow-induced nucleation in polymer melts
,” Faraday Discuss.
144
, 71
–92
(2010
).14.
Kurelec
, L.
, S.
Rastogi
, R.
Meier
, and P.
Lemstra
, “Chain mobility in polymer systems: On the borderline between solid and melt. 3. Phase transformations in nascent ultrahigh molecular weight polyethylene reactor powder at elevated pressure as revealed by in situ Raman spectroscopy
,” Macromolecules
33
, 5593
–5601
(2000
).15.
Somani
, R. H.
, B. S.
Hsiao
, A.
Nogales
, H.
Fruitwala
, S.
Srinivas
, and A. H.
Tsou
, “Structure development during shear flow induced crystallization of i-PP: In situ wide-angle X-ray diffraction study
,” Macromolecules
34
, 5902
–5909
(2001
).16.
Sun
, X.
, H.
Li
, J.
Wang
, and S.
Yan
, “Shear-induced interfacial structure of isotactic polypropylene (iPP) in iPP/fiber composites
,” Macromolecules
39
, 8720
–8726
(2006
).17.
García Gutiérrez
, M.-C.
, G. C.
Alfonso
, C.
Riekel
, and F.
Azzurri
, “Spatially resolved flow-induced crystallization precursors in isotactic polystyrene by simultaneous small-and wide-angle X-ray microdiffraction
,” Macromolecules
37
, 478
–485
(2004
).18.
Balzano
, L.
, N.
Kukalyekar
, S.
Rastogi
, G. W.
Peters
, and J. C.
Chadwick
, “Crystallization and dissolution of flow-induced precursors
,” Phys. Rev. Lett.
100
, 048302
(2008
).19.
Ma
, Z.
, L.
Balzano
, and G. W.
Peters
, “Pressure quench of flow-induced crystallization precursors
,” Macromolecules
45
, 4216
–4224
(2012
).20.
Nazari
, B.
, A. M.
Rhoades
, R. P.
Schaake
, and R. H.
Colby
, “Flow-induced crystallization of peek: Isothermal crystallization kinetics and lifetime of flow-induced precursors during isothermal annealing
,” ACS Macro Lett.
5
, 849
–853
(2016
).21.
Hamad
, F. G.
, R. H.
Colby
, and S. T.
Milner
, “Lifetime of flow-induced precursors in isotactic polypropylene
,” Macromolecules
48
, 7286
–7299
(2015
).22.
Pennings
, A. J.
, and A. M.
Kiel
, “Fractionation of polymers by crystallization from solution, III. On the morphology of fibrillar polyethylene crystals grown in solution
,” Colloid Polym. Sci.
205
, 160
–162
(1965
).23.
Kimata
, S.
, T.
Sakurai
, Y.
Nozue
, T.
Kasahara
, N.
Yamaguchi
, T.
Karino
, M.
Shibayama
, and J. A.
Kornfield
, “Molecular basis of the shish-kebab morphology in polymer crystallization
,” Science
316
, 1014
–1017
(2007
).24.
Hsiao
, B. S.
, L.
Yang
, R. H.
Somani
, C. A.
Avila-Orta
, and L.
Zhu
, “Unexpected shish-kebab structure in a sheared polyethylene melt
,” Phys. Rev. Lett.
94
, 117802
(2005
).25.
Ma
, Z.
, L.
Balzano
, and G. W.
Peters
, “Dissolution and re-emergence of flow-induced shish in polyethylene with a broad molecular weight distribution
,” Macromolecules
49
, 2724
–2730
(2016
).26.
Yang
, H.-R.
, J.
Lei
, L.
Li
, Q.
Fu
, and Z.-M.
Li
, “Formation of interlinked shish-kebabs in injection-molded polyethylene under the coexistence of lightly cross-linked chain network and oscillation shear flow
,” Macromolecules
45
, 6600
–6610
(2012
).27.
Hu
, W.
, D.
Frenkel
, and V. B.
Mathot
, “Simulation of shish-kebab crystallite induced by a single prealigned macromolecule
,” Macromolecules
35
, 7172
–7174
(2002
).28.
Hamad
, F. G.
, R. H.
Colby
, and S. T.
Milner
, “Transition in crystal morphology for flow-induced crystallization of isotactic polypropylene
,” Macromolecules
49
, 5561
–5575
(2016
).29.
Flory
, P. J.
, “Thermodynamics of crystallization in high polymers. I. Crystallization induced by stretching
,” J. Chem. Phys.
15
, 397
–408
(1947
).30.
Yeh
, G.
, and K.
Hong
, “Strain
‐
induced crystallization, Part III: Theory
,” Polym. Eng. Sci.
19
, 395
–400
(1979
).31.
Coppola
, S.
, N.
Grizzuti
, and P. L.
Maffettone
, “Microrheological modeling of flow-induced crystallization
,” Macromolecules
34
, 5030
–5036
(2001
).32.
Tian
, N.
, W.
Zhou
, K.
Cui
, Y.
Liu
, Y.
Fang
, X.
Wang
, L.
Liu
, and L.
Li
, “Extension flow induced crystallization of poly (ethylene oxide)
,” Macromolecules
44
, 7704
–7712
(2011
).33.
Zhu
, S.
, Z.
Wang
, F.
Su
, W.
Zhou
, N.
Tian
, X.
Li
, and L.
Li
, “The influence of inertia and elastic retraction on flow-induced crystallization of isotactic polypropylene
,” J. Rheol.
57
, 1281
–1296
(2013
).34.
Wang
, S.-Q.
, S.
Ravindranath
, Y.
Wang
, and P.
Boukany
, “New theoretical considerations in polymer rheology: Elastic breakdown of chain entanglement network
,” J. Chem. Phys.
127
, 064903
(2007
).35.
Zhou
, W.
, K.
Cui
, N.
Tian
, D.
Liu
, Y.
Liu
, L.
Meng
, X.
Li
, J.
He
, L.
Li
, and X.
Li
, “Disentanglement decelerating flow-induced nucleation
,” Polymer
54
, 942
–947
(2013
).36.
Okura
, M.
, O. O.
Mykhaylyk
, and A. J.
Ryan
, “Effect of matrix polymer on flow-induced nucleation in polymer blends
,” Phys. Rev. Lett.
110
, 087801
(2013
).37.
Keum
, J. K.
, F.
Zuo
, and B. S.
Hsiao
, “Formation and stability of shear-induced shish-kebab structure in highly entangled melts of UHMWPE/HDPE blends
,” Macromolecules
41
, 4766
–4776
(2008
).38.
Kanaya
, T.
, G.
Matsuba
, Y.
Ogino
, K.
Nishida
, H. M.
Shimizu
, T.
Shinohara
, T.
Oku
, J.
Suzuki
, and T.
Otomo
, “Hierarchic structure of shish-kebab by neutron scattering in a wide Q range
,” Macromolecules
40
, 3650
–3654
(2007
).39.
Elmoumni
, A.
, R. A.
Gonzalez-Ruiz
, E. B.
Coughlin
, and H. H.
Winter
, “Isotactic poly (propylene) crystallization: Role of small fractions of high or low molecular weight polymer
,” Macromol. Chem. Phys.
206
, 125
–134
(2005
).40.
Zhong
, G.-J.
, L.
Li
, E.
Mendes
, D.
Byelov
, Q.
Fu
, and Z.-M.
Li
, “Suppression of skin-core structure in injection-molded polymer parts by in situ incorporation of a microfibrillar network
,” Macromolecules
39
, 6771
–6775
(2006
).41.
Xu
, J.-Z.
, C.
Chen
, Y.
Wang
, H.
Tang
, Z.-M.
Li
, and B. S.
Hsiao
, “Graphene nanosheets and shear flow induced crystallization in isotactic polypropylene nanocomposites
,” Macromolecules
44
, 2808
–2818
(2011
).42.
Haggenmueller
, R.
, J. E.
Fischer
, and K. I.
Winey
, “Single wall carbon nanotube/polyethylene nanocomposites: Nucleating and templating polyethylene crystallites
,” Macromolecules
39
, 2964
–2971
(2006
).43.
Byelov
, D.
, P.
Panine
, K.
Remerie
, E.
Biemond
, G. C.
Alfonso
, and W. H.
de Jeu
, “Crystallization under shear in isotactic polypropylene containing nucleators
,” Polymer
49
, 3076
–3083
(2008
).44.
Hwang
, W. R.
, G. W.
Peters
, M. A.
Hulsen
, and H. E.
Meijer
, “Modeling of flow-induced crystallization of particle-filled polymers
,” Macromolecules
39
, 8389
–8398
(2006
).45.
Phillips
, A. W.
, A.
Bhatia
, P.-W.
Zhu
, and G.
Edward
, “Shish formation and relaxation in sheared isotactic polypropylene containing nucleating particles
,” Macromolecules
44
, 3517
–3528
(2011
).46.
Balzano
, L.
, S.
Rastogi
, and G. W.
Peters
, “Crystallization and precursors during fast short-term shear
,” Macromolecules
42
, 2088
–2092
(2009
).47.
Heeley
, E. L.
, C. M.
Fernyhough
, R. S.
Graham
, P. D.
Olmsted
, N. J.
Inkson
, J.
Embery
, D. J.
Groves
, T. C.
McLeish
, A. C.
Morgovan
, and F.
Meneau
, “Shear-induced crystallization in blends of model linear and long-chain branched hydrogenated polybutadienes
,” Macromolecules
39
, 5058
–5071
(2006
).48.
Ma
, Z.
, L.
Balzano
, T.
van Erp
, G.
Portale
, and G. W.
Peters
, “Short-term flow induced crystallization in isotactic polypropylene: How short is short?
,” Macromolecules
46
, 9249
–9258
(2013
).49.
Seki
, M.
, D. W.
Thurman
, J. P.
Oberhauser
, and J. A.
Kornfield
, “Shear-mediated crystallization of isotactic polypropylene: The role of long chain-long chain overlap
,” Macromolecules
35
, 2583
–2594
(2002
).50.
Cui
, K.
, L.
Meng
, N.
Tian
, W.
Zhou
, Y.
Liu
, Z.
Wang
, J.
He
, and L.
Li
, “Self-acceleration of nucleation and formation of shish in extension-induced crystallization with strain beyond fracture
,” Macromolecules
45
, 5477
–5486
(2012
).51.
Shen
, B.
, Y.
Liang
, J. A.
Kornfield
, and C. C.
Han
, “Mechanism for shish formation under shear flow: An interpretation from an in situ morphological study
,” Macromolecules
46
, 1528
–1542
(2013
).52.
Mykhaylyk
, O. O.
, C. M.
Fernyhough
, M.
Okura
, J. P. A.
Fairclough
, A. J.
Ryan
, and R.
Graham
, “Monodisperse macromolecules—A stepping stone to understanding industrial polymers
,” Eur. Polym. J.
47
, 447
–464
(2011
).53.
Wang
, Y.
, X.
Li
, X.
Zhu
, and S.-Q.
Wang
, “Characterizing state of chain entanglement in entangled polymer solutions during and after large shear deformation
,” Macromolecules
45
, 2514
–2521
(2012
).54.
Thien
, N. P.
, and R. I.
Tanner
, “A new constitutive equation derived from network theory
,” J. Non-Newtonian Fluid Mech.
2
, 353
–365
(1977
).55.
Housmans
, J.-W.
, R. J. A.
Steenbakkers
, P. C.
Roozemond
, G. W. M.
Peters
, and H. E. H.
Meijer
, “Saturation of pointlike nuclei and the transition to oriented structures in flow-induced crystallization of isotactic polypropylene
,” Macromolecules
42
, 5728
–5740
(2009
).56.
Liu
, Y.
, W.
Zhou
, K.
Cui
, N.
Tian
, X.
Wang
, L.
Liu
, L.
Li
, and Y.
Zhou
, “Extensional rheometer for in situ x-ray scattering study on flow-induced crystallization of polymer
,” Rev. Sci. Instrum.
82
, 045104
(2011
).57.
Mezghani
, K.
, and P. J.
Phillips
, “The γ-phase of high molecular weight isotactic polypropylene: III. The equilibrium melting point and the phase diagram
,” Polymer
39
, 3735
–3744
(1998
).58.
Bach
, A.
, K.
Almdal
, H. K.
Rasmussen
, and O.
Hassager
, “Elongational viscosity of narrow molar mass distribution polystyrene
,” Macromolecules
36
, 5174
–5179
(2003
).59.
Nielsen
, J. K.
, H. K.
Rasmussen
, O.
Hassager
, and G. H.
McKinley
, “Elongational viscosity of monodisperse and bidisperse polystyrene melts
,” J. Rheol.
50
, 453
–476
(2006
).60.
van Meerveld
, J.
, G. W.
Peters
, and M.
Hütter
, “Towards a rheological classification of flow induced crystallization experiments of polymer melts
,” Rheol. Acta
44
, 119
–134
(2004
).61.
Yaoita
, T.
, T.
Isaki
, Y.
Masubuchi
, H.
Watanabe
, G.
Ianniruberto
, and G.
Marrucci
, “Primitive chain network simulation of elongational flows of entangled linear chains: Role of finite chain extensibility
,” Macromolecules
44
, 9675
–9682
(2011
).62.
McKinley
, G. H.
, and O.
Hassager
, “The Considere condition and rapid stretching of linear and branched polymer melts
,” J. Rheol.
43
, 1195
–1212
(1999
).63.
Doi
, M.
, and S. F.
Edwards
, The Theory of Polymer Dynamics
(Oxford University
, Oxford
, 1988
).64.
Coccorullo
, I.
, R.
Pantani
, and G.
Titomanlio
, “Spherulitic nucleation and growth rates in an iPP under continuous shear flow
,” Macromolecules
41
, 9214
–9223
(2008
).65.
Zuidema
, H.
, G. W. M.
Peters
, and H. E. H.
Meijer
, “Development and validation of a recoverable strain-based model for flow-induced crystallization of polymers
,” Macromol. Theory Simul.
10
, 447
–460
(2001
).66.
Toki
, S.
, I.
Sics
, S.
Ran
, L.
Liu
, B. S.
Hsiao
, S.
Murakami
, K.
Senoo
, and S.
Kohjiya
, “New insights into structural development in natural rubber during uniaxial deformation by in situ synchrotron X-ray diffraction
,” Macromolecules
35
, 6578
–6584
(2002
).© 2017 The Society of Rheology.
2017
The Society of Rheology
You do not currently have access to this content.