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Investigations Into The Origins Of Plastic Flow And Strain Hardening In Amorphous Glassy Polymers

Jatin, V. Sudarkodi, Sumit Basu
Published 2014 · Materials Science

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Abstract In this work, through well designed molecular dynamics (MD) simulations on carefully equilibrated macromolecular ensembles of a generic model of an amorphous glassy polymer, we attempt to understand the origins of plasticity in these materials. In particular, we are interested in the phenomena of post yield strain softening and strain hardening that are typical of these materials. The intrinsic uniaxial stress–strain behaviour is characterized by an elastic part, yield followed by strain-softening and hardening at large strains. Existing constitutive theories of glassy polymers rely on the so called rubber elastic analogy where strain hardening is assumed to be the result of the affine orientation and subsequent stretching of an underlying entanglement network. Using MD simulations and a continuum thermo-mechanical framework, we isolate the plastic free energy associated with the energetic back-stress that governs hardening. We show that the hardening owes its origin to the non-bonded part of the forcefield and is related to the increase in the number of close binary contacts between parts of macromolecular chains that are pushed into close proximity due to compressive deformation. The strain softening is a result of a burst of free volume evolution that accompanies a sudden unstable volume expansion occurring right after yield as the polymer undergoes a deformation induced disordering. This is accompanied by a sharp increase in the room available for changes in dihedral conformations. These conformational changes are mainly responsible for accommodating the plastic deformation as many of them are unable to flip back to their original conformations even after unloading. Finally, by fitting the uniaxial responses obtained from the MD simulations with a standard constitutive model, we show that the barriers between the torsional states govern the small strain behaviour while the strength of the non-bonded interactions govern hardening.
This paper references
10.1006/JCPH.1995.1039
Fast parallel algorithms for short-range molecular dynamics
S. Plimpton (1993)
10.1002/POLB.23199
Rate- and Temperature-Dependent Strain Softening in Solid Polymers
L. V. Breemen (2012)
Large inelastic deformation of glassy polymers
M. Boyce (1986)
10.1021/MA00008A056
Molecular dynamics simulation of an amorphous polymer under tension. 1. Phenomenology
D. Brown (1991)
10.1063/1.474564
Molecular-dynamics simulation of moisture diffusion in polyethylene beyond 10 ns duration
M. Fukuda (1997)
10.1016/0001-6160(79)90055-5
Plastic deformation in metallic glasses
A. S. Argon (1979)
10.1088/0965-0393/14/4/002
A molecular dynamics study on the strength and ductility of high Tg polymers
A. Negi (2006)
10.1126/SCIENCE.288.5463.116
Chain mobility in the amorphous region of nylon 6 observed under active uniaxial deformation
Lôo (2000)
10.1063/1.3450318
Interaction between physical aging, deformation, and segmental mobility in poly(methyl methacrylate) glasses.
Hau-Nan Lee (2010)
10.1002/POLB.20384
Identifying the primitive path mesh in entangled polymer liquids
Sathish K. Sukumaran (2004)
10.1063/1.475686
Molecular dynamics simulation of water diffusion in atactic and amorphous isotactic polypropylene
M. Fukuda (1998)
10.1103/PhysRevE.80.031803
Topological analysis of polymeric melts: chain-length effects and fast-converging estimators for entanglement length.
R. Hoy (2009)
10.1002/POLB.1989.090270210
Fourier transform infrared study of conformational changes occurring at the yield point in uniaxially drawn polymers
Z. Xu (1989)
10.1103/PHYSREVB.24.4091
Dispersion of relaxation rates in dense liquids and glasses
M. H. Cohen (1981)
10.1007/BF00281393
Allgemeine Kontinuumstheorie der Versetzungen und Eigenspannungen
E. Kröner (1959)
10.1007/BF01105270
Video-controlled tensile testing of polymers and metals beyond the necking point
C. G'sell (1992)
10.1016/S0749-6419(02)00009-8
A thermo-mechanical study of mode I, small-scale yielding crack-tip fields in glassy polymers
Sumit Basu (2002)
10.1002/POL.1969.160070411
Tensile yield‐stress behavior of glassy polymers
C. Bauwens-Crowet (1969)
10.1080/01418619308213969
Atomistic modelling of plastic deformation of glassy polymers
P. Mott (1993)
10.1016/J.JNONCRYSOL.2006.02.156
Simulation of polymer glasses: From segmental dynamics to bulk mechanics
A. Lyulin (2006)
10.1016/J.IJPLAS.2010.02.004
Necking in glassy polymers: Effects of intrinsic anisotropy and structural evolution kinetics in their viscoplastic flow
H. Li (2010)
10.1080/14786437308220987
A theory for the low-temperature plastic deformation of glassy polymers
A. Argon (1973)
10.1098/rspa.1968.0029
The use of a mathematical model to describe isothermal stress-strain curves in glassy thermoplastics
R. Haward (1968)
10.1063/1.4822570
Understanding Molecular Simulation
D. Frenkel (2001)
10.1016/S0167-6636(97)00006-9
A numerical study of crack-tip plasticity in glassy polymers
J. Lai (1997)
10.5254/1.3538357
A New Constitutive Relation for Rubber
A. Gent (1996)
10.1017/cbo9780511762956
The Mechanics and Thermodynamics of Continua
M. Gurtin (2010)
10.12693/APHYSPOLA.107.690
Relaxation of Free Volume in Polycarbonate and Polystyrene Studied by Positron Annihilation Lifetime Spectroscopy
D. Cangialosi (2005)
Deformation of glassy polymers: Energy storage at early stages of loading
S. Shenogin (2004)
10.1016/J.IJPLAS.2008.11.004
A thermo-mechanically coupled theory for large deformations of amorphous polymers. Part II: Applications
Nicoli M. Ames (2009)
10.1016/0022-5096(93)90043-F
On Improved Network Models for Rubber Elasticity and Their Applications to Orientation Hardening in Glassy Polymers
Peidong Wu (1993)
10.1016/0167-6636(88)90003-8
Large inelastic deformation of glassy polymers. part I: rate dependent constitutive model
M. Boyce (1988)
10.1021/MA00149A018
Detailed molecular structure of a vinyl polymer glass
D. Theodorou (1985)
10.1063/1.1628670
Equilibration of long chain polymer melts in computer simulations
R. Auhl (2003)
10.1115/1.3564580
Elastic-Plastic Deformation at Finite Strains
E. H. Lee (1969)
10.1063/1.1726558
Theory for the Plasticity of Glassy Polymers
R. Robertson (1966)
10.1016/0032-3861(93)90252-6
Energy storage during inelastic deformation of glassy polymers
O. Hasan (1993)
10.1002/POLB.21579
Does the Strain Hardening Modulus of Glassy Polymers Scale with the Flow Stress
L. E. Govaert (2008)
10.1021/MA00057A034
Simulation of elastic and plastic response in the glassy polycarbonate of 4,4'-isopropylidenediphenol
Michelle Hutnik (1993)
10.3390/MET2040488
Comparative Study of Elastoplastic Constitutive Models for Deformation of Metallic Glasses
Ming Zhao (2012)
10.1016/J.IJPLAS.2005.07.006
On modeling the micro-indentation response of an amorphous polymer
L. Anand (2006)
10.1016/J.JMPS.2010.07.015
Ageing and rejuvenation in glassy amorphous polymers
D. Mahajan (2010)
10.1016/S0020-7683(02)00651-0
A theory of amorphous solids undergoing large deformations, with application to polymeric glasses
L. Anand (2003)
10.1088/0965-0393/18/2/025001
Investigations into the applicability of rubber elastic analogy to hardening in glassy polymers
D. Mahajan (2010)
10.1016/0032-3861(72)90042-0
Birefringence of plastically deformed poly(methyl methacrylate)
S. Raha (1972)
10.1103/PHYSREVE.81.011803
Coarse-graining scheme for simulating uniaxial stress-strain response of glassy polymers through molecular dynamics.
M. Majumder (2010)
10.1002/polb.21734
Scaling of the strain hardening modulus of glassy polymers with the flow stress
M. Robbins (2009)
Theory of Non-Newtonian Flow
이태규 (1974)
10.1017/CBO9781139033046
The physics of deformation and fracture of polymers
A. Argon (2013)
10.1063/1.1722098
Theory of Non‐Newtonian Flow. I. Solid Plastic System
T. Ree (1955)
10.1007/S10853-008-2989-Z
A theory for yield phenomenon of glassy polymers based on the strain non-uniformity under loading conditions
G. Spathis (2008)
10.1103/PHYSREVE.82.011803
Void nucleation and disentanglement in glassy amorphous polymers.
D. Mahajan (2010)
10.1016/S0032-3861(03)00112-5
On the origin of strain hardening in glassy polymers
van Hgh Melick (2003)
10.1016/0032-3861(94)90934-2
Evaluation of polymer free volume by positron annihilation and gas diffusivity measurements
Y. Kobayashi (1994)
10.1016/J.IJPLAS.2011.10.002
A large-deformation gradient theory for elastic–plastic materials: Strain softening and regularization of shear bands
L. Anand (2012)
10.1080/14786437708232634
Plastic deformation in polyimides, with new implications on the theory of plastic deformation of glassy polymers
A. Argon (1977)
10.1103/PhysRevLett.99.117801
Strain hardening in polymer glasses: limitations of network models.
R. Hoy (2007)
10.1063/1.3077859
Deforming glassy polystyrene: Influence of pressure, thermal history, and deformation mode on yielding and hardening.
Bart Vorselaars (2009)
10.1088/0953-8984/20/24/244131
Modification of the ageing dynamics of glassy polymers due to a temperature step
M. Warren (2008)
10.1103/PhysRevE.77.031801
Strain hardening of polymer glasses: entanglements, energetics, and plasticity.
R. Hoy (2008)
10.1007/S10853-005-6513-4
Differences in mechanical behavior between alternating and random styrene-methyl methacrylate copolymers
D. Rana (2005)
10.1103/PHYSREVLETT.89.175505
Enhanced mobility accompanies the active deformation of a glassy amorphous polymer.
F. Capaldi (2002)
10.1103/PhysRevE.68.011801
Growth, microstructure, and failure of crazes in glassy polymers.
J. Rottler (2003)
10.1088/0965-0393/14/6/013
A molecular dynamics study of the failure modes of a glassy polymer confined between rigid walls
Udit Kulmi (2006)
10.1002/PEN.11810
On the plastic and viscoelastic behavior of methylmethacrylate-based random copolymers
P. Tordjeman (1997)



This paper is referenced by
10.1007/S11043-016-9336-6
Mechanical characterization and modeling of the deformation and failure of the highly crosslinked RTM6 epoxy resin
X. Morelle (2017)
10.1016/J.IJPLAS.2016.11.011
Constitutive modeling of size effect on deformation behaviors of amorphous polymers in micro-scaled deformation
Y. Deng (2017)
In fl uence of strain rates on the mechanical behaviors of shape memory polymer
Xiaogang Guo (2015)
10.1016/j.ijplas.2020.102751
Incorporating crystallinity distributions into a thermo-mechanically coupled constitutive model for semi-crystalline polymers
S. Felder (2020)
10.1016/j.physa.2019.123763
Parameter study of variable order fractional model for the strain hardening behavior of glassy polymers
Ruifan Meng (2020)
10.1103/physreve.101.022503
Characterization of entanglements in glassy polymeric ensembles using the Gaussian linking number.
Rasool Ahmad (2020)
10.1016/J.IJPLAS.2015.09.004
Enhanced plasticity by nanocrystallite in bulk amorphous Al2O3–ZrO2–Y2O3
Xiqing Xu (2016)
10.1016/J.IJMECSCI.2019.105064
Finite deformation constitutive model for macro-yield behavior of amorphous glassy polymers with a molecular entanglement-based internal-state variable
Han Jiang (2019)
10.1016/J.CERAMINT.2016.11.159
Enhanced plasticity by deformation-induced nanocrysallization in bulk amorphous Al2O3-ZrO2-Y2O3
Xiqing Xu (2017)
10.2514/6.2015-0647
Multiscale analysis of polymer nanocomposites considering hyperelasto-plastic behavior
Hyunseong Shin (2015)
10.1016/J.JALLCOM.2017.01.170
Evaluation of metastable degree in amorphous Al2O3-ZrO2-Y2O3 and its effect on plastic deformation
Xiqing Xu (2017)
10.3390/polym8040077
Static and Dynamic Properties of Semi-Crystalline Polyethylene
Ming-ming Xu (2016)
10.1088/0964-1726/24/9/095009
Influence of strain rates on the mechanical behaviors of shape memory polymer
X. Guo (2015)
10.1088/1361-651X/AA7341
High fidelity computational characterization of the mechanical response of thermally aged polycarbonate
Z. Zhang (2017)
10.1039/C6RA07191K
One-pot, mouldable, thermoplastic resins from poly(propylene carbonate) and poly(caprolactone triol)
S. Spoljaric (2016)
Mechanical characterization and modeling of the deformation and failure of the highly cross-linked RTM 6 epoxy resin
X. Morelle (2019)
10.1016/J.JMPS.2019.01.008
A constitutive model for strain hardening behavior of predeformed amorphous polymers: Incorporating dissipative dynamics of molecular orientation
R. Xiao (2019)
10.1016/J.MECHMAT.2019.103100
Fatigue analysis of brittle polymers via Fourier transform of the stress
Valerian Hirschberg (2019)
10.1016/J.IJPLAS.2015.09.011
On couple-stress elasto-plastic constitutive frameworks for glassy polymers
F. Alisafaei (2016)
10.1016/j.polymer.2020.122908
All-atom molecular dynamics study of impact fracture of glassy polymers. II: Microscopic origins of stresses in elasticity, yielding, and strain hardening
Zhiye Tang (2020)
10.1088/1361-651X/AA9EE4
Mechanical response of two polyimides through coarse-grained molecular dynamics simulations
V. Sudarkodi (2017)
10.1016/J.JMPS.2018.08.014
Unveiling the nanoscale heterogeneity controlled deformation of thermosets
J. Chevalier (2018)
10.1016/J.POLYMER.2017.12.055
Influences of the molecular structures of curing agents on the inelastic-deformation mechanisms in highly-crosslinked epoxy polymers
Hyungbum Park (2018)
10.1002/MAME.201500322
A Macro‐Damaged Viscoelastoplastic Model for Thermomechanical and Rate‐Dependent Behavior of Glassy Polymers
P. Yu (2016)
10.1039/c9sm01848d
Compression-induced anti-nematic order in glassy and semicrystalline polymers.
S. Jabbari-Farouji (2019)
10.1007/978-3-319-23419-9_10
The Procter and Gamble Company: Current State and Future Needs in Materials Modeling
Russell DeVane (2016)
10.1002/pol.20200130
Effect of molecular structure of curing agents on cyclic creep in highly cross‐linked epoxy polymers
Hyungbum Park (2020)
10.1007/S00466-018-1663-9
Variable-order fractional description of compression deformation of amorphous glassy polymers
Ruifan Meng (2019)
10.1007/s11666-018-0769-0
Low-Temperature Transformation of Amorphous Sol–Gel TiO2 Powder to Anatase During Cold Spray Deposition
A. Baszczuk (2018)
10.1016/j.ijplas.2020.102680
Multiscale micromorphic theory compatible with MD simulations in both time-scale and length-scale
C. Park (2020)
10.1016/j.jmps.2020.103962
A multiscale framework for the elasto-plastic constitutive equations of crosslinked epoxy polymers considering the effects of temperature, strain rate, hydrostatic pressure, and crosslinking density
Hyungbum Park (2020)
10.1103/PhysRevMaterials.4.035601
Relaxation time of a polymer glass stretched at very large strains
R. Sahli (2020)
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