Chemical crosslinking, physical associating, and filler filling play vital roles in nonlinear responses of rubbers under large amplitude oscillatory shear (LAOS). Herein, a systematical investigation was performed for polyisoprene rubber vulcanizates and compounds on the framework of LAOS analytical methods to quantify intra- and intercycle nonlinearities. It is shown that the Payne effect is featured by intercycle strain softening and intracycle hardening. Furthermore, chemical crosslinking and intermolecular association cause marked shear thickening at the medium range of rate amplitude, which is related to the nonideally crosslinked structures from numerical studies. Fillers can promote nonlinear viscoelastic behaviors. In compounds, modulus recovery during cyclic oscillatory shear deformation is not directly related to the reorganization of the filler phase, which is testified by simultaneous measurements of rheological responses and electrical resistivity during increasing-decreasing amplitude sweep cycles.
REFERENCES
1.
Kumar
, S. K.
, B. C.
Benicewicz
, R. A.
Vaia
, and K. I.
Winey
, “50th anniversary perspective: Are polymer nanocomposites practical for applications?
” Macromolecules
50
, 714
–731
(2017
). 2.
Akiba
, M.
, and A.
Hashim
, “Vulcanization and crosslinking in elastomers
,” Prog. Polym. Sci.
22
, 475
–521
(1997
). 3.
Chen
, Q.
, S.
Gong
, J.
Moll
, D.
Zhao
, S. K.
Kumar
, and R. H.
Colby
, “Mechanical reinforcement of polymer nanocomposites from percolation of a nanoparticle network
,” ACS Macro Lett.
4
, 398
–402
(2015
). 4.
Gusev
, A. A
., “Micromechanical mechanism of reinforcement and losses in filled rubbers
,” Macromolecules
39
, 5960
–5962
(2006
). 5.
Payne
, A. R
., “The dynamic properties of carbon black-loaded natural rubber vulcanizates. Part I
,” J. Appl. Polym. Sci.
6
, 57
–63
(1962
). 6.
Payne
, A. R
., “The dynamic properties of carbon black-loaded natural rubber vulcanizates. Part II
,” J. Appl. Polym. Sci.
6
, 368
–372
(1962
). 7.
Chazeau
, L.
, J.
Brown
, L.
Yanyo
, and S.
Sternstein
, “Modulus recovery kinetics and other insights into the Payne effect for filled elastomers
,” Polym. Compos.
21
, 202
–222
(2000
). 8.
Hyun
, K.
, S. H.
Kim
, K. H.
Ahn
, and S. J.
Lee
, “Large amplitude oscillatory shear as a way to classify the complex fluids
,” J. Non-Newton. Fluid Mech.
107
, 51
–65
(2002
). 9.
Fan
, X.
, H.
Xu
, Q.
Zhang
, Y.
Song
, and Q.
Zheng
, “Insight into the weak strain overshoot of carbon black filled natural rubber
,” Polymer
167
, 109
–117
(2019
). 10.
Xu
, H.
, X.
Xia
, M.
Hussain
, Y.
Song
, and Q.
Zheng
, “Linear and nonlinear rheological behaviors of silica filled nitrile butadiene rubber
,” Polymer
156
, 222
–227
(2018
). 11.
Papon
, A.
, S.
Merabia
, L.
Guy
, F.
Lequeux
, H.
Montes
, P.
Sotta
, and D. R.
Long
, “Unique nonlinear behavior of nano-filled elastomers: From the onset of strain softening to large amplitude shear deformations
,” Macromolecules
45
, 2891
–2904
(2012
). 12.
Meera
, A. P.
, S.
Said
, Y.
Grohens
, and S.
Thomas
, “Nonlinear viscoelastic behavior of silica-filled natural rubber nanocomposites
,” J. Phys. Chem. C
113
, 17997
–18002
(2009
). 13.
Martinetti
, L.
, O.
Carey-De La Torre
, K. S.
Schweizer
, and R. H.
Ewoldt
, “Inferring the nonlinear mechanisms of a reversible network
,” Macromolecules
51
, 8772
–8789
(2018
). 14.
Hyun
, K.
, M.
Wilhelm
, C. O.
Klein
, K. S.
Cho
, J. G.
Nam
, K. H.
Ahn
, S. J.
Lee
, R. H.
Ewoldt
, and G. H.
McKinley
, “A review of nonlinear oscillatory shear tests: Analysis and application of large amplitude oscillatory shear (LAOS)
,” Prog. Polym. Sci.
36
, 1697
–1753
(2011
). 15.
Ewoldt
, R. H.
, A.
Hosoi
, and G. H.
McKinley
, “New measures for characterizing nonlinear viscoelasticity in large amplitude oscillatory shear
,” J. Rheol.
52
, 1427
–1458
(2008
). 16.
Xiong
, W.
, and X.
Wang
, “Linear-nonlinear dichotomy of rheological responses in particle-filled polymer melts
,” J. Rheol.
62
, 171
–181
(2018
). 17.
Robertson
, C. G.
, and X.
Wang
, “Isoenergetic jamming transition in particle-filled systems
,” Phys. Rev. Lett.
95
, 075703
(2005
). 18.
Heinrich
, G.
, and M.
Klüppel
, Recent advances in the theory of filler networking in elastomers
, in Filled Elastomers Drug Delivery Systems
, edited by S. L.
Kwang
(Springer
, Berlin
, 2002
).19.
Lin
, C. R.
, and Y. D.
Lee
, “Strain-dependent dynamic properties of filled rubber network systems
,” Macromol. Theory Simul.
5
, 1075
–1104
(1996
). 20.
Meier
, J. G.
, and M.
Klüppel
, “Carbon black networking in elastomers monitored by dynamic mechanical and dielectric spectroscopy
,” Macromol. Mater. Eng.
293
, 12
–38
(2008
). 21.
Niedermeier
, W.
, J.
Frohlich
, and H. D.
Luginsland
, “Reinforcement mechanism in the rubber matrix by active fillers
,” Kautsch. Gummi Kunstst.
55
, 356
–356
(2002
).22.
Funt
, J
., “Dynamic testing and reinforcement of rubber
,” Rubber Chem. Technol.
61
, 842
–865
(1988
). 23.
Maier
, P.
, and D.
Goritz
, “Molecular interpretation of the Payne effect
,” Kautsch. Gummi Kunstst.
49
, 18
–21
(1996
).24.
Song
, Y.
, L.
Zeng
, and Q.
Zheng
, “Reconsideration of the rheology of silica filled natural rubber compounds
,” J. Phys. Chem. B
121
, 5867
–5875
(2017
). 25.
Wilhelm
, M
., “Fourier-transform rheology
,” Macromol. Mater. Eng.
287
, 83
–105
(2002
). 26.
Giacomin
, A. J.
, and J. M.
Dealy
, Large-amplitude oscillatory shear
, in Techniques in Rheological Measurement
(Springer
, Dordrecht
, 1993
).27.
Bird
, R. B.
, R. C.
Armstrong
, and O.
Hassager
, Dynamics of Polymeric Liquids. Vol. 1: Fluid Mechanics
(Wiley
, New York, 1987
).28.
Hyun
, K.
, J. G.
Nam
, M.
Wilhelm
, K. H.
Ahn
, and S. J.
Lee
, “Nonlinear response of complex fluids under LAOS (large amplitude oscillatory shear) flow
,” Korea-Aust. Rheol. J.
15
, 97
–105
(2003
).29.
Hatzikiriakos
, S. G.
, and J. M.
Dealy
, “Role of slip and fracture in the oscillating flow of HDPE in a capillary
,” J. Rheol.
36
, 845
–884
(1992
). 30.
Hyun
, K.
, and W.
Kim
, “A new non-linear parameter Q from FT-rheology under nonlinear dynamic oscillatory shear for polymer melts system
,” Korea-Aust. Rheol. J.
23
, 227
–235
(2011
). 31.
Neidhöfer
, T.
, M.
Wilhelm
, and B.
Debbaut
, “Fourier-transform rheology experiments and finite-element simulations on linear polystyrene solutions
,” J. Rheol.
47
, 1351
–1371
(2003
). 32.
Cho
, K. S.
, K.
Hyun
, K. H.
Ahn
, and S. J.
Lee
, “A geometrical interpretation of large amplitude oscillatory shear response
,” J. Rheol.
49
, 747
–758
(2005
). 33.
Ewoldt
, R. H.
, P.
Winter
, J.
Maxey
, and G. H.
McKinley
, “Large amplitude oscillatory shear of pseudoplastic and elastoviscoplastic materials
,” Rheol. Acta
49
, 191
–212
(2010
). 34.
Bharadwaj
, N. A.
, and R. H.
Ewoldt
, “Constitutive model fingerprints in medium-amplitude oscillatory shear
,” J. Rheol.
59
, 557
–592
(2015
). 35.
Martinetti
, L.
, and R. H.
Ewoldt
, “Time-strain separability in medium-amplitude oscillatory shear
,” Phys. Fluids
31
, 021213
(2019
). 36.
Leblanc
, J. L
., “Nonlinear viscoelastic characterization of molten thermoplastic vulcanizates (TPV) through large amplitude harmonic experiments
,” Rheol. Acta
46
, 1013
–1027
(2007
). 37.
Leblanc
, J. L
., “Investigating the non-linear viscoelastic behavior of filled rubber compounds through Fourier transform rheometry
,” Rubber Chem. Technol.
78
, 54
–75
(2005
). 38.
Leblanc
, J. L.
, and C.
de la Chapelle
, “Characterizing gum elastomers by Fourier transform rheometry
,” Rubber Chem. Technol.
76
, 979
–1000
(2003
). 39.
Ulmer
, J
., “Strain dependence of dynamic mechanical properties of carbon black-filled rubber compounds
,” Rubber Chem. Technol.
69
, 15
–47
(1996
). 40.
Hyun
, K.
, H. T.
Lim
, and K. H.
Ahn
, “Nonlinear response of polypropylene (PP)/clay nanocomposites under dynamic oscillatory shear flow
,” Korea-Aust. Rheol. J.
24
, 113
–120
(2012
). 41.
Tanaka
, F.
, and S.
Edwards
, “Viscoelastic properties of physically crosslinked networks: Part 1. Non-linear stationary viscoelasticity
,” J. Non-Newton. Fluid Mech.
43
, 247
–271
(1992
). 42.
Tanaka
, F.
, and S.
Edwards
, “Viscoelastic properties of physically crosslinked networks: Part 2. Dynamic mechanical moduli
,” J. Non-Newton. Fluid Mech.
43
, 273
–288
(1992
). 43.
Leblanc
, J. L
., “Large amplitude oscillatory shear experiments to investigate the nonlinear viscoelastic properties of highly loaded carbon black rubber compounds without curatives
,” J. Appl. Polym. Sci.
109
, 1271
–1293
(2008
). 44.
Sugimoto
, M.
, Y.
Suzuki
, K.
Hyun
, K. H.
Ahn
, T.
Ushioda
, A.
Nishioka
, T.
Taniguchi
, and K.
Koyama
, “Melt rheology of long-chain-branched polypropylenes
,” Rheol. Acta
46
, 33
–44
(2006
). 45.
Leblanc
, J. L.
, and C.
de la Chapelle
, “Updating a torsional dynamic rheometer for Fourier transform rheometry on rubber materials
,” Rubber Chem. Technol.
76
, 287
–298
(2003
). 46.
Curro
, J. G.
, D. S.
Pearson
, and E.
Helfand
, “Viscoelasticity of randomly crosslinked polymer networks. Relaxation of dangling chains
,” Macromolecules
18
, 1157
–1162
(1985
). 47.
Kraus
, G.
, and J.
Dugone
, “Adsorption of elastomers on carbon black
,” Ind. Eng. Chem. Res.
47
, 1809
–1816
(1955
). 48.
Ianniruberto
, G.
, and G.
Marrucci
, “Convective constraint release (CCR) revisited
,” J. Rheol.
58
, 89
–102
(2014
). 49.
Des Cloizeaux
, J
., “Relaxation and viscosity anomaly of melts made of long entangled polymers: Time-dependent reptation
,” Macromolecules
23
, 4678
–4687
(1990
). 50.
Van Ruymbeke
, E.
, R.
Keunings
, V.
Stéphenne
, A.
Hagenaars
, and C.
Bailly
, “Evaluation of reptation models for predicting the linear viscoelastic properties of entangled linear polymers
,” Macromolecules
35
, 2689
–2699
(2002
). 51.
Liu
, C.
, P.
Liu
, Q.
Chen
, B.
Du
, and Z.
Wang
, “Entanglement relaxation of poly(1-butene) and its copolymer with ethylene detected in conventional shear rheometer and quartz resonator
,” J. Rheol.
63
, 167
–177
(2019
). 52.
Ianniruberto
, G.
, and G.
Marrucci
, “Convective orientational renewal in entangled polymers
,” J. Non-Newton. Fluid Mech.
95
, 363
–374
(2000
). 53.
Furuichi
, K.
, C.
Nonomura
, Y.
Masubuchi
, and H.
Watanabe
, “Chain contraction and nonlinear stress damping in primitive chain network simulations
,” J. Chem. Phys.
133
, 174902
(2010
). 54.
Saphiannikova
, M.
, V.
Toshchevikov
, I.
Gazuz
, F.
Petry
, S.
Westermann
, and G.
Heinrich
, “Multiscale approach to dynamic-mechanical analysis of unfilled rubbers
,” Macromolecules
47
, 4813
–4823
(2014
). 55.
Vega
, D. A.
, L. R.
Gómez
, L. E.
Roth
, J. A.
Ressia
, M. A.
Villar
, and E. M.
Vallés
, “Arm retraction potential of branched polymers in the absence of dynamic dilution
,” Phys. Rev. Lett.
95
, 166002
(2005
). 56.
Davidson
, J. D.
, and N.
Goulbourne
, “A nonaffine network model for elastomers undergoing finite deformations
,” J. Mech. Phys. Solids
61
, 1784
–1797
(2013
). 57.
Agudelo
, D. C.
, L. E.
Roth
, D. A.
Vega
, E. M.
Vallés
, and M. A.
Villar
, “Dynamic response of transiently trapped entanglements in polymer networks
,” Polymer
55
, 1061
–1069
(2014
). 58.
Sarvestani
, A. S
., “On the emergence of the Payne effect in polymer melts reinforced with nanoparticles
,” Macromol. Theory Simul.
25
, 312
–321
(2016
). 59.
Marrucci
, G.
, and G.
Ianniruberto
, “Flow-induced orientation and stretching of entangled polymers
,” Philos. Trans. R. Soc. A
361
, 677
–688
(2003
). 60.
Masubuchi
, Y
., “Multichain slip-spring simulations for branch polymers
,” Macromolecules
51
, 10184
–10193
(2018
). 61.
Roth
, L. E.
, D. C.
Agudelo
, J. A.
Ressia
, L. R.
Gómez
, E. M.
Vallés
, M. A.
Villar
, and D. A.
Vega
, “Viscoelastic response of linear defects trapped in polymer networks
,” Eur. Polym. J.
64
, 1
–9
(2015
). 62.
Xu
, H.
, X.
Fan
, Y.
Song
, and Q.
Zheng
. “Reinforcement and Payne effect of hydrophobic silica filled natural rubber nanocomposites
,” Compos. Sci. Technol.
187
, 107943
(2019
). 63.
Tanaka
, Y
., “Structural characterization of natural polyisoprenes: Solve the mystery of natural rubber based on structural study
,” Rubber Chem. Technol.
74
, 355
–375
(2001
). 64.
Tarachiwin
, L.
, J.
Sakdapipanich
, K.
Ute
, T.
Kitayama
, T.
Bamba
, E.-i.
Fukusaki
, A.
Kobayashi
, and Y.
Tanaka
, “Structural characterization of α-terminal group of natural rubber. 1. Decomposition of branch-points by lipase and phosphatase treatments
,” Biomacromolecules
6
, 1851
–1857
(2005
). 65.
Tarachiwin
, L.
, J.
Sakdapipanich
, K.
Ute
, T.
Kitayama
, and Y.
Tanaka
, “Structural characterization of α-terminal group of natural rubber. 2. Decomposition of branch-points by phospholipase and chemical treatments
,” Biomacromolecules
6
, 1858
–1863
(2005
). 66.
Mongruel
, A.
, and M.
Cartault
, “Nonlinear rheology of styrene-butadiene rubber filled with carbon-black or silica particles
,” J. Rheol.
50
, 115
–135
(2006
). 67.
Majesté
, J.-C.
, and F.
Vincent
, “A kinetic model for silica-filled rubber reinforcement
,” J. Rheol.
59
, 405
–427
(2015
). 68.
Domurath
, J.
, M.
Saphiannikova
, G.
Ausias
, and G.
Heinrich
, “Modelling of stress and strain amplification effects in filled polymer melts
,” J. Non-Newton. Fluid Mech.
171
, 8
–16
(2012
). 69.
Huber
, G.
, and T. A.
Vilgis
, “Universal properties of filled rubbers: Mechanisms for reinforcement on different length scales
,” Kautsch. Gummi Kunstst.
52
, 102
–107
(1999
).70.
Klüppel
, M.
, The role of disorder in filler reinforcement of elastomers on various length scales
, in Filler-Reinforced Elastomers/Scanning Force Microscopy
(Springer
, Berlin
, 2003
).71.
Potanin
, A.
, and W.
Russel
, “Fractal model of consolidation of weakly aggregated colloidal dispersions
,” Phys. Rev. E
53
, 3702
(1996
). 72.
Kantor
, Y.
, and I.
Webman
, “Elastic properties of random percolating systems
,” Phys. Rev. Lett.
52
, 1891
(1984
). 73.
Arbabi
, S.
, and M.
Sahimi
, “Elastic properties of three-dimensional percolation networks with stretching and bond-bending forces
,” Phys. Rev. B
38
, 7173
(1988
). 74.
Loiseau
, A.
, and J.-F.
Tassin
, “Model nanocomposites based on laponite and poly(ethylene oxide): Preparation and rheology
,” Macromolecules
39
, 9185
–9191
(2006
). 75.
Balberg
, I
., “Tunneling and nonuniversal conductivity in composite materials
,” Phys. Rev. Lett.
59
, 1305
(1987
). 76.
Payne
, A.
, and R.
Whittaker
, “Dynamic properties of materials
,” Rheol. Acta
9
, 97
–102
(1970
). 77.
Wang
, X.
, and C. G.
Robertson
, “Strain-induced nonlinearity of filled rubbers
,” Phys. Rev. E
72
, 031406
(2005
). 78.
Han
, H.
, Y.
Song
, and Q.
Zheng
. “Rheological and interfacial properties of colloidal electrolytes
,” Chin. J. Polym. Sci.
37
, 1039
–1044
(2019
) 79.
Litvinov
, V.
, and P.
Steeman
, “EPDM-carbon black interactions and the reinforcement mechanisms, as studied by low-resolution 1H NMR
,” Macromolecules
32
, 8476
–8490
(1999
). 80.
Schwartz
, G. A.
, S.
Cerveny
, A. J.
Marzocca
, M.
Gerspacher
, and L.
Nikiel
, “Thermal aging of carbon black filled rubber compounds. I. Experimental evidence for bridging flocculation
,” Polymer
44
, 7229
–7240
(2003
). 81.
See supplementary material at https://10.1122/1.5124034 for the experimental rheological responses of IR systems and characterization results for filler dispersity, swelling, molecular weight, and electrical resistivity.
© 2020 The Society of Rheology.
2020
The Society of Rheology
You do not currently have access to this content.
