Linear and nonlinear rheology and structural relaxation in dense glassy and jammed soft repulsive pNIPAM microgel suspensions

Ghosh, Ashesh; Chaudhary, Gaurav; Kang, Jin Gu; Braun, Paul V.; Ewoldt, Randy H.; Schweizer, Kenneth S.

doi:10.1039/C8SM02014K

Linear and nonlinear rheology and structural relaxation in dense glassy and jammed soft repulsive pNIPAM microgel suspensions

Journal Article · Wed Dec 26 00:00:00 EST 2018 · Soft Matter

DOI:https://doi.org/10.1039/C8SM02014K· OSTI ID:1634191

^[1]; ^[2]; Kang, Jin Gu ^[2]; ^[2]; ^[2]; Schweizer, Kenneth S. ^[2]

Univ. of Illinois at Urbana-Champaign (United States); University of Illinois.at Urbana-Champaign
Univ. of Illinois at Urbana-Champaign (United States)

We present an integrated experimental and quantitative theoretical study of the mechanics of self-crosslinked, slightly charged, repulsive pNIPAM microgel suspensions over a very wide range of concentrations (c) that span the fluid, glassy and putative “soft jammed” regimes. In the glassy regime we measure a linear elastic dynamic shear modulus over 3 decades which follows an apparent power law concentration dependence G' ~ c^5.64, a variation that appears distinct from prior studies of crosslinked ionic microgel suspensions. At very high concentrations there is a sharp crossover to a nearly linear growth of the modulus. To theoretically understand these observations, we formulate an approach to address all three regimes within a single conceptual Brownian dynamics framework. A minimalist single particle description is constructed that allows microgel size to vary with concentration due to steric de-swelling effects. Using a Hertzian repulsion interparticle potential and a suite of statistical mechanical theories, quantitative predictions under quiescent conditions of microgel collective structure, dynamic localization length, elastic modulus, and the structural relaxation time are made. Based on a constant inter-particle repulsion strength parameter which is determined by requiring the theory to reproduce the linear elastic shear modulus over the entire concentration regime, we demonstrate good agreement between theory and experiment. Testable predictions are then made. We also measured nonlinear rheological properties with a focus on the yield stress and strain. A theoretical analysis with no adjustable parameters predicts how the quiescent structural relaxation time changes under deformation, and how the yield stress and strain change as a function of concentration. Reasonable agreement with our observations is obtained. To the best of our knowledge, this is the first attempt to quantitatively understand structure, quiescent relaxation and shear elasticity, and nonlinear yielding of dense microgel suspensions using microscopic force based theoretical methods that include activated hopping processes. Here, we expect our approach will be useful for other soft polymeric particle suspensions in the core–shell family.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-07ER46471

OSTI ID:: 1634191

Alternate ID(s):: OSTI ID: 1491277

Journal Information:: Soft Matter, Journal Name: Soft Matter Journal Issue: 5 Vol. 15; ISSN SMOABF; ISSN 1744-683X

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Microgel particles as model colloids: theory, properties and applications Saunders, Brian R.; Vincent, Brian Advances in Colloid and Interface Science, Vol. 80, Issue 1 https://doi.org/10.1016/S0001-8686(98)00071-2	journal	February 1999
Tunable rheology of dense soft deformable colloids Vlassopoulos, Dimitris; Cloitre, Michel Current Opinion in Colloid & Interface Science, Vol. 19, Issue 6 https://doi.org/10.1016/j.cocis.2014.09.007	journal	December 2014
Cross-Linker-Free N -Isopropylacrylamide Gel Nanospheres Gao, Jun; Frisken, Barbara J. Langmuir, Vol. 19, Issue 13 https://doi.org/10.1021/la0269762	journal	June 2003
Influence of Reaction Conditions on the Synthesis of Self-Cross-Linked N -Isopropylacrylamide Microgels Gao, Jun; Frisken, Barbara J. Langmuir, Vol. 19, Issue 13 https://doi.org/10.1021/la034207s	journal	June 2003
Nonlinear Elasticity and Yielding of Nanoparticle Glasses Rao, Ranjeet B.; Kobelev, Vladmir L.; Li, Qi Langmuir, Vol. 22, Issue 6 https://doi.org/10.1021/la052740x	journal	March 2006
Doubly Temperature Sensitive Core−Shell Microgels Berndt, Ingo; Richtering, Walter Macromolecules, Vol. 36, Issue 23 https://doi.org/10.1021/ma034771+	journal	October 2003
Dynamical Theory of Segmental Relaxation and Emergent Elasticity in Supercooled Polymer Melts Mirigian, Stephen; Schweizer, Kenneth S. Macromolecules, Vol. 48, Issue 6 https://doi.org/10.1021/ma5022083	journal	March 2015
Liquid-State Theory of Semidilute and Concentrated Polymer Solutions Chatterjee, Avik P.; Schweizer, Kenneth S. Macromolecules, Vol. 31, Issue 7 https://doi.org/10.1021/ma971460o	journal	April 1998
Phase behaviour of concentrated suspensions of nearly hard colloidal spheres Pusey, P. N.; van Megen, W. Nature, Vol. 320, Issue 6060 https://doi.org/10.1038/320340a0	journal	March 1986
Thermal vestige of the zero-temperature jamming transition Zhang, Zexin; Xu, Ning; Chen, Daniel T. N. Nature, Vol. 459, Issue 7244 https://doi.org/10.1038/nature07998	journal	May 2009
A micromechanical model to predict the flow of soft particle glasses Seth, Jyoti R.; Mohan, Lavanya; Locatelli-Champagne, Clémentine Nature Materials, Vol. 10, Issue 11 https://doi.org/10.1038/nmat3119	journal	September 2011
Does size matter? Elasticity of compressed suspensions of colloidal- and granular-scale microgels Menut, Paul; Seiffert, Sebastian; Sprakel, Joris Soft Matter, Vol. 8, Issue 1 https://doi.org/10.1039/C1SM06355C	journal	January 2012
Ultrasoft, highly deformable microgels Bachman, Haylee; Brown, Ashley C.; Clarke, Kimberly C. Soft Matter, Vol. 11, Issue 10 https://doi.org/10.1039/C5SM00047E	journal	January 2015
The glass and jamming transitions of soft polyelectrolyte microgel suspensions Pellet, Charlotte; Cloitre, Michel Soft Matter, Vol. 12, Issue 16 https://doi.org/10.1039/C5SM03001C	journal	January 2016
Swelling, structure, and phase stability of compressible microgels Urich, Matthew; Denton, Alan R. Soft Matter, Vol. 12, Issue 44 https://doi.org/10.1039/C6SM02056A	journal	January 2016
Long-term aging behaviors in a model soft colloidal system Li, Qi; Peng, Xiaoguang; McKenna, Gregory B. Soft Matter, Vol. 13, Issue 7 https://doi.org/10.1039/C6SM02408D	journal	January 2017
Design of yield-stress fluids: a rheology-to-structure inverse problem Nelson, Arif Z.; Ewoldt, Randy H. Soft Matter, Vol. 13, Issue 41 https://doi.org/10.1039/C7SM00758B	journal	January 2017
Dynamics and rheology of colloidal star polymers Erwin, Brian M.; Cloitre, Michel; Gauthier, Mario Soft Matter, Vol. 6, Issue 12 https://doi.org/10.1039/b926526k	journal	January 2010
Fluid–solid transitions in soft-repulsive colloids Paloli, Divya; Mohanty, Priti S.; Crassous, Jérôme J. Soft Matter, Vol. 9, Issue 11 https://doi.org/10.1039/c2sm27654b	journal	January 2013
Elasticity of compressed microgel suspensions Romeo, Giovanni; Ciamarra, Massimo Pica Soft Matter, Vol. 9, Issue 22 https://doi.org/10.1039/c3sm50222h	journal	January 2013
Rheology of soft colloids across the onset of rigidity: scaling behavior, thermal, and non-thermal responses Basu, Anindita; Xu, Ye; Still, Tim Soft Matter, Vol. 10, Issue 17 https://doi.org/10.1039/c3sm52454j	journal	January 2014
Transport coefficients in glassy colloidal fluids Saltzman, Erica J.; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 119, Issue 2 https://doi.org/10.1063/1.1578633	journal	July 2003
Microscopic theory of gelation and elasticity in polymer–particle suspensions Chen, Yeng-Long; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 120, Issue 15 https://doi.org/10.1063/1.1683077	journal	April 2004
High‐Frequency Elastic Moduli of Simple Fluids Zwanzig, Robert; Mountain, Raymond D. The Journal of Chemical Physics, Vol. 43, Issue 12 https://doi.org/10.1063/1.1696718	journal	December 1965
Nonlinear elasticity and yielding of depletion gels Kobelev, Vladimir; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 123, Issue 16 https://doi.org/10.1063/1.2109887	journal	October 2005
Derivation of a microscopic theory of barriers and activated hopping transport in glassy liquids and suspensions Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 123, Issue 24 https://doi.org/10.1063/1.2137701	journal	December 2005
Glassy dynamics and mechanical response in dense fluids of soft repulsive spheres. I. Activated relaxation, kinetic vitrification, and fragility Yang, Jian; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 134, Issue 20 https://doi.org/10.1063/1.3592563	journal	May 2011
Glassy dynamics and mechanical response in dense fluids of soft repulsive spheres. II. Shear modulus, relaxation-elasticity connections, and rheology Yang, Jian; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 134, Issue 20 https://doi.org/10.1063/1.3592565	journal	May 2011
Theory of nonlinear elasticity, stress-induced relaxation, and dynamic yielding in dense fluids of hard nonspherical colloids Zhang, Rui; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 136, Issue 15 https://doi.org/10.1063/1.3701661	journal	April 2012
Effective interactions between soft-repulsive colloids: Experiments, theory, and simulations Mohanty, Priti S.; Paloli, Divya; Crassous, Jérôme J. The Journal of Chemical Physics, Vol. 140, Issue 9 https://doi.org/10.1063/1.4866644	journal	March 2014
Elastically cooperative activated barrier hopping theory of relaxation in viscous fluids. I. General formulation and application to hard sphere fluids Mirigian, Stephen; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 140, Issue 19 https://doi.org/10.1063/1.4874842	journal	May 2014
Elastically cooperative activated barrier hopping theory of relaxation in viscous fluids. II. Thermal liquids Mirigian, Stephen; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 140, Issue 19 https://doi.org/10.1063/1.4874843	journal	May 2014
The physics of the colloidal glass transition Hunter, Gary L.; Weeks, Eric R. Reports on Progress in Physics, Vol. 75, Issue 6 https://doi.org/10.1088/0034-4885/75/6/066501	journal	May 2012
Ageing and yield behaviour in model soft colloidal glasses Christopoulou, C.; Petekidis, G.; Erwin, B. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 367, Issue 1909 https://doi.org/10.1098/rsta.2009.0166	journal	December 2009
Elasticity and clustering in concentrated depletion gels Ramakrishnan, S.; Chen, Y. -L.; Schweizer, K. S. Physical Review E, Vol. 70, Issue 4 https://doi.org/10.1103/PhysRevE.70.040401	journal	October 2004
Strain softening, yielding, and shear thinning in glassy colloidal suspensions Kobelev, Vladimir; Schweizer, Kenneth S. Physical Review E, Vol. 71, Issue 2 https://doi.org/10.1103/PhysRevE.71.021401	journal	February 2005
Glass Formation and Shear Elasticity in Dense Suspensions of Repulsive Anisotropic Particles Kramb, R. C.; Zhang, R.; Schweizer, K. S. Physical Review Letters, Vol. 105, Issue 5 https://doi.org/10.1103/PhysRevLett.105.055702	journal	July 2010
Observation of a glass transition in suspensions of spherical colloidal particles Pusey, P. N.; van Megen, W. Physical Review Letters, Vol. 59, Issue 18 https://doi.org/10.1103/PhysRevLett.59.2083	journal	November 1987
Anomalous Viscous Loss in Emulsions Liu, Andrea J.; Ramaswamy, Sriram; Mason, T. G. Physical Review Letters, Vol. 76, Issue 16 https://doi.org/10.1103/PhysRevLett.76.3017	journal	April 1996
Yield stress materials in soft condensed matter Bonn, Daniel; Denn, Morton M.; Berthier, Ludovic Reviews of Modern Physics, Vol. 89, Issue 3 https://doi.org/10.1103/RevModPhys.89.035005	journal	August 2017
Elastic properties of soft particle pastes Seth, Jyoti R.; Cloitre, Michel; Bonnecaze, Roger T. Journal of Rheology, Vol. 50, Issue 3 https://doi.org/10.1122/1.2186982	journal	May 2006
Jamming and overpacking fuzzy microgels: Deformation, interpenetration, and compression Conley, Gaurasundar M.; Aebischer, Philippe; Nöjd, Sofi Science Advances, Vol. 3, Issue 10 https://doi.org/10.1126/sciadv.1700969	journal	October 2017
Molecular Theories of Segmental Dynamics and Mechanical Response in Deeply Supercooled Polymer Melts and Glasses Chen, Kang; Saltzman, Erica J.; Schweizer, Kenneth S. Annual Review of Condensed Matter Physics, Vol. 1, Issue 1 https://doi.org/10.1146/annurev-conmatphys-070909-104110	journal	August 2010
Tunable dynamic fragility and elasticity in dense suspensions of many-arm-star polymer colloids Yang, Jian; S. Schweizer, Kenneth EPL (Europhysics Letters), Vol. 90, Issue 6 https://doi.org/10.1209/0295-5075/90/66001	journal	June 2010
The Physics of the Colloidal Glass Transition Hunter, Gary L.; Weeks, Eric R. arXiv https://doi.org/10.48550/arxiv.1106.3581	text	January 2011
Elastically Cooperative Activated Barrier Hopping Theory of Relaxation in Viscous Fluids. I. General Formulation and Application to Hard Sphere Fluids Mirigian, Stephen; Schweizer, Kenneth S. arXiv https://doi.org/10.48550/arxiv.1402.5124	text	January 2014
Swelling, Structure, and Phase Stability of Compressible Microgels Urich, Matthew; Denton, Alan R. arXiv https://doi.org/10.48550/arxiv.1610.05295	text	January 2016

Cited By (3)

Directed Printing and Reconfiguration of Thermoresponsive Silica‐pNIPAM Nanocomposites Guo, Yusheng; Belgodere, Jorge A.; Ma, Yingzhen Macromolecular Rapid Communications https://doi.org/10.1002/marc.201900191	journal	June 2019
Directed Printing and Reconfiguration of Thermoresponsive Silica-pNIPAM Nanocomposites Guo, Yusheng; Belgodere, Jorge A.; Ma, Yingzhen Macromolecular Rapid Communications, Vol. 40, Issue 13 https://doi.org/10.1002/marc.201970028	journal	July 2019
Flow properties reveal the particle-to-polymer transition of ultra-low crosslinked microgels Scotti, Andrea; Brugnoni, Monia; G. Lopez, Carlos Soft Matter, Vol. 16, Issue 3 https://doi.org/10.1039/c9sm01451a	journal	January 2020