TY - JOUR
T1 - Expanding the application of the van Gurp-Palmen plot
T2 - New insights into polymer melt rheology
AU - Qian, Zhiyuan
AU - McKenna, Gregory B.
N1 - Funding Information:
The authors would like to thank Yuya Doi and Dimitris Vlassopoulos for providing the rheological data for the linear PS and ring PS, Frank S. Bates for providing the rheological data for the graft polymers, and Jacques Roovers for sharing the dynamic data on the PS combs. Christian Friedrich is thanked for help in obtaining original data. We thank H. Henning Winter for making the IRIS software available to us. We also thank the Texas Tech University Graduate School and the John R. Bradford endowment at Texas Tech University for support of the project.
Publisher Copyright:
© 2018 Elsevier Ltd
PY - 2018/10/24
Y1 - 2018/10/24
N2 - We report on an extension of the van Gurp-Palmen (vGP) plot [van Gurp, M. and Palmen, J., Rheology Bulletin, 1998, 67(1), 5–8.] developed through a compilation of literature data for polymer melts with different topological structures: linear (pure and blend), ring, comb, and bottlebrush. We introduce a new parameter: the reciprocal of complex modulus at the first minimum moving from the terminal regime (1/Gδmin,1 ∗) and compare it with the steady-state recoverable compliance Js. Results show that 1/Gδmin,1 ∗ and Js while related to each other in that they follow similar dependences on the molecular weight (linear and bottlebrush polymers), weight fraction of high molecular weight content (linear blends), and backbone concentration (comb polymer), there are also differences. For example, in the unentangled regime both Js and 1/Gδmin,1 ∗ increase with increasing molecular weight but reach different plateau values as entanglement coupling sets in. In the case of ring polymers, the molecular weight dependences of 1/Gδmin,1 ∗(∼Mw 1) and Js(∼Mw 2) show very different scaling with molecular weight and do not reach a plateau value even for molecular weights as high as approximately 15 times the entanglement molecular weight of the linear counterpart. Furthermore, examination of the impact of linear additives on the vGP plots of the rings potentially provides a new way to assess their freedom from linear contamination. Also, because 1/Gδmin,1 ∗ occurs in the frequency regime above that of the terminal regime and Js requires either very good estimates of terminal behavior in dynamic measurements or direct determination from creep and recovery measurements, 1/Gδmin,1 ∗ is easier to obtain. The work shows that detailed analysis of the van Gurp-Palmen plot has the potential to provide new insights into the rheological response of polymer melts over what is obtained conventionally from viscoelastic characterization methods.
AB - We report on an extension of the van Gurp-Palmen (vGP) plot [van Gurp, M. and Palmen, J., Rheology Bulletin, 1998, 67(1), 5–8.] developed through a compilation of literature data for polymer melts with different topological structures: linear (pure and blend), ring, comb, and bottlebrush. We introduce a new parameter: the reciprocal of complex modulus at the first minimum moving from the terminal regime (1/Gδmin,1 ∗) and compare it with the steady-state recoverable compliance Js. Results show that 1/Gδmin,1 ∗ and Js while related to each other in that they follow similar dependences on the molecular weight (linear and bottlebrush polymers), weight fraction of high molecular weight content (linear blends), and backbone concentration (comb polymer), there are also differences. For example, in the unentangled regime both Js and 1/Gδmin,1 ∗ increase with increasing molecular weight but reach different plateau values as entanglement coupling sets in. In the case of ring polymers, the molecular weight dependences of 1/Gδmin,1 ∗(∼Mw 1) and Js(∼Mw 2) show very different scaling with molecular weight and do not reach a plateau value even for molecular weights as high as approximately 15 times the entanglement molecular weight of the linear counterpart. Furthermore, examination of the impact of linear additives on the vGP plots of the rings potentially provides a new way to assess their freedom from linear contamination. Also, because 1/Gδmin,1 ∗ occurs in the frequency regime above that of the terminal regime and Js requires either very good estimates of terminal behavior in dynamic measurements or direct determination from creep and recovery measurements, 1/Gδmin,1 ∗ is easier to obtain. The work shows that detailed analysis of the van Gurp-Palmen plot has the potential to provide new insights into the rheological response of polymer melts over what is obtained conventionally from viscoelastic characterization methods.
KW - Complex modulus
KW - Polymer topology
KW - Steady-state recoverable compliance
KW - van Gurp-Palmen plot
UR - http://www.scopus.com/inward/record.url?scp=85054639985&partnerID=8YFLogxK
U2 - 10.1016/j.polymer.2018.09.036
DO - 10.1016/j.polymer.2018.09.036
M3 - Article
AN - SCOPUS:85054639985
VL - 155
SP - 208
EP - 217
JO - Polymer
JF - Polymer
SN - 0032-3861
ER -