Photo-oxidation of semicrystalline polymers: Effect of stress triaxiality on ductility

Cundiff, K. N.; Morgeneyer, T. F.; Benzerga, A. A.

doi:10.1016/j.tmater.2025.100048

Photo-oxidation of semicrystalline polymers: Effect of stress triaxiality on ductility

Journal Article · Wed Jan 08 00:00:00 EST 2025 · Tomography of Materials and Structures

DOI:https://doi.org/10.1016/j.tmater.2025.100048· OSTI ID:2502146

Cundiff, K. N. ^[1]; ^[2]; Benzerga, A. A. ^[3]

Texas A & M Univ., College Station, TX (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
PSL University, Evry (France). MINES Paris
Texas A & M Univ., College Station, TX (United States)

The effect of stress triaxiality on the strain-to-fracture of as-received and photo-oxidized polyamide-6 (PA-6) was investigated using mechanical testing, synchrotron X-ray tomography, and finite element analyses. Mechanical tests were conducted on cylindrical and round notched specimens, where different notch radii were used to vary the stress triaxiality. The specimens were aged by exposure to ultra-violet (UV) radiation at 60∘, causing photo-oxidation. As-received and so-aged specimens were loaded to failure (complete loss of load carrying capacity). For both unaged and aged specimens, a higher triaxiality led to a lower strain-to-fracture. To elucidate the micromechanical damage that mediates fracture in both conditions, specimens with an intermediate notch sharpness were loaded to the peak load, unloaded, and scanned ex situ using synchrotron X-ray tomography. Damage in the unaged bar was found to occur by cavitation and was concentrated at the center of the specimen, where the triaxiality is highest. In the UV-aged bar, a network of inter-connected chemical cracks were found on the notch surface, where the triaxiality is lowest. Finite element analyses were deployed to approximate the local triaxiality at damaged regions in the unaged and UV-aged specimens using a constitutive relation for semicrystalline polymers. From these analyses, the relationship between local triaxiality and strain-to-fracture was quantified for both unaged and photo-oxidized PA-6. Both unaged and photo-oxidized PA-6 showed similar decreases in ductility with triaxiality, hinting at common ductile fracture processes.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: Qatar National Research Fund (NPRP); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2502146

Report Number(s):: SAND2025--00374J

Journal Information:: Tomography of Materials and Structures, Journal Name: Tomography of Materials and Structures Journal Issue: 1 Vol. 7; ISSN 2949-673X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (73)

Thermooxidative aging of polyoxymethylene, part 2: Embrittlement mechanisms Fayolle, B.; Verdu, J.; Piccoz, D. Journal of Applied Polymer Science, Vol. 111, Issue 1 https://doi.org/10.1002/app.29126	journal	October 2008
Finite element implementation of a macromolecular viscoplastic polymer model Kweon, S.; Benzerga, A. A. International Journal for Numerical Methods in Engineering, Vol. 94, Issue 10 https://doi.org/10.1002/nme.4474	journal	April 2013
Damage of semicrystalline polyamide 6 assessed by 3D X‐ray tomography: From microstructural evolution to constitutive modeling Laiarinandrasana, L.; Morgeneyer, T. F.; Proudhon, H. Journal of Polymer Science Part B: Polymer Physics, Vol. 48, Issue 13 https://doi.org/10.1002/polb.22043	journal	May 2010
Video-controlled tensile testing of polymers and metals beyond the necking point G'Sell, C.; Hiver, J. M.; Dahoun, A. Journal of Materials Science, Vol. 27, Issue 18 https://doi.org/10.1007/BF01105270	journal	January 1992
The effect of weathering on residual stresses and mechanical properties in injection-moulded semi-crystalline polymers Qayyum, M. M.; White, J. R. Journal of Materials Science, Vol. 21, Issue 7 https://doi.org/10.1007/BF01114283	journal	July 1986
Structure and plastic deformation of polyethylene Lin, L.; Argon, A. S. Journal of Materials Science, Vol. 29, Issue 2 https://doi.org/10.1007/BF01162485	journal	January 1994
Mechanical behavior of polyamide-6 after combined photo-oxidative and hygrothermal aging Cundiff, K. N.; Rodriguez, A. K.; Benzerga, A. A. Colloid and Polymer Science, Vol. 302, Issue 4 https://doi.org/10.1007/s00396-023-05218-7	journal	December 2023
Embrittlement of polypropylene fibre during thermal oxidation Fayolle, Bruno; Richaud, Emmanuel; Verdu, Jacques Journal of Materials Science, Vol. 43, Issue 3 https://doi.org/10.1007/s10853-007-2242-1	journal	November 2007
Review: degradation-induced embrittlement in semi-crystalline polymers having their amorphous phase in rubbery state Fayolle, Bruno; Richaud, Emmanuel; Colin, Xavier Journal of Materials Science, Vol. 43, Issue 22 https://doi.org/10.1007/s10853-008-3005-3	journal	November 2008
Oxidation-induced stiffening versus weakening in semicrystalline polymers Rodriguez, A. K.; Mansoor, B.; Benzerga, A. A. Journal of Materials Science, Vol. 59, Issue 12 https://doi.org/10.1007/s10853-023-08843-3	journal	September 2023
Effect of Stress Triaxiality on the Flow and Fracture of Mg Alloy AZ31 Kondori, Babak; Benzerga, A. Amine Metallurgical and Materials Transactions A, Vol. 45, Issue 8 https://doi.org/10.1007/s11661-014-2211-7	journal	February 2014
Neck propagation Hutchinson, J. W.; Neale, K. W. Journal of the Mechanics and Physics of Solids, Vol. 31, Issue 5 https://doi.org/10.1016/0022-5096(83)90007-8	journal	January 1983
A three-dimensional constitutive model for the large stretch behavior of rubber elastic materials Arruda, Ellen M.; Boyce, Mary C. Journal of the Mechanics and Physics of Solids, Vol. 41, Issue 2 https://doi.org/10.1016/0022-5096(93)90013-6	journal	February 1993
On improved network models for rubber elasticity and their applications to orientation hardening in glassy polymers Wu, P. D.; Van Der Giessen, E. Journal of the Mechanics and Physics of Solids, Vol. 41, Issue 3 https://doi.org/10.1016/0022-5096(93)90043-F	journal	March 1993
Plastic fracture in weathered polymers Qayyum, M. M.; White, J. R. Polymer, Vol. 28, Issue 3 https://doi.org/10.1016/0032-3861(87)90201-1	journal	March 1987
Photo-oxidation of thick polymer samples—Part II: The influence of oxygen diffusion on the natural and artificial weathering of polyolefins Cunliffe, A. V.; Davis, A. Polymer Degradation and Stability, Vol. 4, Issue 1 https://doi.org/10.1016/0141-3910(82)90003-9	journal	January 1982
Low temperature thermo-oxidation of thermoplastics in the solid state Lemaire, Jacques; Arnaud, René; Gardette, Jean-Luc Polymer Degradation and Stability, Vol. 33, Issue 2 https://doi.org/10.1016/0141-3910(91)90021-I	journal	January 1991
A heterogeneous model for the thermal oxidation of solid polypropylene from chemiluminescence analysis Celina, M.; George, G. A. Polymer Degradation and Stability, Vol. 40, Issue 3 https://doi.org/10.1016/0141-3910(93)90138-9	journal	January 1993
Physical spreading of oxidation in solid polypropylene as studied by chemiluminescence Celina, M.; George, G. A.; Billingham, N. C. Polymer Degradation and Stability, Vol. 42, Issue 3 https://doi.org/10.1016/0141-3910(93)90229-C	journal	January 1993
Chemiluminescence imaging of the oxidation of polypropylene Celina, M.; George, G. A.; Lacey, D. J. Polymer Degradation and Stability, Vol. 47, Issue 2 https://doi.org/10.1016/0141-3910(94)00134-T	journal	January 1995
Heterogeneous and homogeneous kinetic analyses of the thermal oxidation of polypropylene Celina, M.; George, G. A. Polymer Degradation and Stability, Vol. 50, Issue 1 https://doi.org/10.1016/0141-3910(95)00136-A	journal	January 1995
Large inelastic deformation of glassy polymers. part I: rate dependent constitutive model Boyce, Mary C.; Parks, David M.; Argon, Ali S. Mechanics of Materials, Vol. 7, Issue 1 https://doi.org/10.1016/0167-6636(88)90003-8	journal	September 1988
Crystallization and melting behaviour of photodegraded polypropylene — I. Chemi-crystallization Rabello, M. S.; White, J. R. Polymer, Vol. 38, Issue 26 https://doi.org/10.1016/S0032-3861(97)00213-9	journal	January 1997
Scanning force microscopic investigation of plasticity and damage mechanisms in polypropylene spherulites under simple shear Coulon, G.; Castelein, G.; G'Sell, C. Polymer, Vol. 40, Issue 1 https://doi.org/10.1016/S0032-3861(98)00221-3	journal	January 1999
Ductile Fracture by Void Growth to Coalescence Benzerga, A. Amine; Leblond, Jean-Baptiste Advances in Applied Mechanics https://doi.org/10.1016/S0065-2156(10)44003-X	book	January 2010
Improvement of the mechanical properties of photo-oxidized films after recycling La Mantia, F. P.; Gardette, J. L. Polymer Degradation and Stability, Vol. 75, Issue 1 https://doi.org/10.1016/S0141-3910(01)00199-9	journal	January 2002
Comparison of the UV-degradation chemistry of polypropylene, polyethylene, polyamide 6 and polybutylene terephthalate Gijsman, Pieter; Meijers, Guido; Vitarelli, Giacomo Polymer Degradation and Stability, Vol. 65, Issue 3 https://doi.org/10.1016/S0141-3910(99)00033-6	journal	September 1999
The study of mechanical properties in sheaf-structured spherulite semi-crystalline polymers using a data-driven micromechanical model Jiang, Chenxu; Zhou, Jia; Cui, Jiaxin Computational Materials Science, Vol. 237 https://doi.org/10.1016/j.commatsci.2024.112915	journal	March 2024
Polymer ageing: physics, chemistry or engineering? Time to reflect White, Jim R. Comptes Rendus Chimie, Vol. 9, Issue 11-12 https://doi.org/10.1016/j.crci.2006.07.008	journal	November 2006
Temperature dependent mechanical behaviour of PVDF: Experiments and numerical modelling Laiarinandrasana, L.; Besson, J.; Lafarge, M. International Journal of Plasticity, Vol. 25, Issue 7 https://doi.org/10.1016/j.ijplas.2008.09.008	journal	July 2009
Effects of crystal content on the mechanical behaviour of polyethylene under finite strains: Experiments and constitutive modelling Ayoub, G.; Zaïri, F.; Fréderix, C. International Journal of Plasticity, Vol. 27, Issue 4 https://doi.org/10.1016/j.ijplas.2010.07.005	journal	April 2011
Plastic yielding of semicrystalline polymers affected by amorphous phase Rozanski, Artur; Galeski, Andrzej International Journal of Plasticity, Vol. 41 https://doi.org/10.1016/j.ijplas.2012.07.008	journal	February 2013
Three dimensional quantification of anisotropic void evolution in deformed semi-crystalline polyamide 6 Laiarinandrasana, Lucien; Klinkova, Olga; Nguyen, Franck International Journal of Plasticity, Vol. 83 https://doi.org/10.1016/j.ijplas.2016.04.001	journal	August 2016
An experimental methodology to characterise post-necking behaviour and quantify ductile damage accumulation in isotropic materials Sancho, A.; Cox, M. J.; Cartwright, T. International Journal of Solids and Structures, Vol. 176-177 https://doi.org/10.1016/j.ijsolstr.2019.06.010	journal	November 2019
Modeling the viscoplastic behavior of a semicrystalline polymer Cundiff, K. N.; Ayoub, G.; Benzerga, A. A. International Journal of Solids and Structures, Vol. 254-255 https://doi.org/10.1016/j.ijsolstr.2022.111920	journal	November 2022
Relative influence of microstructure and macroscopic triaxiality on cavitation damage in a semi-crystalline polymer Castagnet, Sylvie; Deburck, Yann Materials Science and Engineering: A, Vol. 448, Issue 1-2 https://doi.org/10.1016/j.msea.2006.11.100	journal	March 2007
Effect of photo-oxidation cracks on behaviour of thick polypropylene samples Yakimets, Iryna; Lai, Dawei; Guigon, Michèle Polymer Degradation and Stability, Vol. 86, Issue 1 https://doi.org/10.1016/j.polymdegradstab.2004.01.013	journal	October 2004
Mechanism of degradation induced embrittlement in polyethylene Fayolle, B.; Colin, X.; Audouin, L. Polymer Degradation and Stability, Vol. 92, Issue 2 https://doi.org/10.1016/j.polymdegradstab.2006.11.012	journal	February 2007
Mechanism of the temperature-dependent degradation of polyamide 66 films exposed to water Gonçalves, Elsa Silva; Poulsen, Lars; Ogilby, Peter R. Polymer Degradation and Stability, Vol. 92, Issue 11 https://doi.org/10.1016/j.polymdegradstab.2007.08.007	journal	November 2007
A new kinetic model for predicting polyamide 6-6 hydrolysis and its mechanical embrittlement El-Mazry, C.; Correc, O.; Colin, X. Polymer Degradation and Stability, Vol. 97, Issue 6 https://doi.org/10.1016/j.polymdegradstab.2012.03.003	journal	June 2012
Thermal oxidation kinetics of additive free polyamide 6-6 El-Mazry, C.; Ben Hassine, M.; Correc, O. Polymer Degradation and Stability, Vol. 98, Issue 1 https://doi.org/10.1016/j.polymdegradstab.2012.11.002	journal	January 2013
Review: Auto-oxidation of aliphatic polyamides Richaud, Emmanuel; Okamba Diogo, Octavie; Fayolle, Bruno Polymer Degradation and Stability, Vol. 98, Issue 9 https://doi.org/10.1016/j.polymdegradstab.2013.04.012	journal	September 2013
Review of polymer oxidation and its relationship with materials performance and lifetime prediction Celina, Mathew C. Polymer Degradation and Stability, Vol. 98, Issue 12 https://doi.org/10.1016/j.polymdegradstab.2013.06.024	journal	December 2013
Molecular and macromolecular structure changes in polyamide 11 during thermal oxidation Okamba-Diogo, Octavie; Richaud, Emmanuel; Verdu, Jacques Polymer Degradation and Stability, Vol. 108 https://doi.org/10.1016/j.polymdegradstab.2014.05.028	journal	October 2014
Influence of temperature and stabilization on oxygen diffusion limited oxidation profiles of polyamide 6 Gijsman, Pieter; Dong, Weifu; Quintana, Adam Polymer Degradation and Stability, Vol. 130 https://doi.org/10.1016/j.polymdegradstab.2016.05.024	journal	August 2016
Polyethylene loss of ductility during oxidation: Effect of initial molar mass distribution Reano, Armando F.; Guinault, Alain; Richaud, Emmanuel Polymer Degradation and Stability, Vol. 149 https://doi.org/10.1016/j.polymdegradstab.2018.01.021	journal	March 2018
Diffusion-limited oxidation of polyamide: Three stages of fracture behavior Wei, Xin-Feng; Kallio, Kai J.; Bruder, Stefan Polymer Degradation and Stability, Vol. 154 https://doi.org/10.1016/j.polymdegradstab.2018.05.024	journal	August 2018
Prediction of stress induced by heterogeneous oxidation: Case of epoxy/amine networks Ernault, Esteve; Dirrenberger, Justin; Richaud, Emmanuel Polymer Degradation and Stability, Vol. 162 https://doi.org/10.1016/j.polymdegradstab.2019.02.019	journal	April 2019
Effect of UV-aging on the mechanical and fracture behavior of low density polyethylene Rodriguez, A. K.; Mansoor, B.; Ayoub, G. Polymer Degradation and Stability, Vol. 180 https://doi.org/10.1016/j.polymdegradstab.2020.109185	journal	October 2020
Probing into the microstructural evolution of isotactic polypropylene during photo-oxidation degradation Wu, Hao; Zhao, Ying; Dong, Xia Polymer Degradation and Stability, Vol. 183 https://doi.org/10.1016/j.polymdegradstab.2020.109434	journal	January 2021
Origin of embrittlement in Polyamide 6 induced by chemical degradations: mechanisms and governing factors Deshoulles, Q.; Le Gall, M.; Dreanno, C. Polymer Degradation and Stability, Vol. 191 https://doi.org/10.1016/j.polymdegradstab.2021.109657	journal	September 2021
Chemical coupling between oxidation and hydrolysis in polyamide 6 - A key aspect in the understanding of microplastic formation Deshoulles, Q.; Le Gall, M.; Dreanno, C. Polymer Degradation and Stability, Vol. 197 https://doi.org/10.1016/j.polymdegradstab.2022.109851	journal	March 2022
Diffusion-limited hydrolysis in polymeric materials Linde, Erik; Giron, Nicholas H.; Celina, Mathew C. Polymer Degradation and Stability, Vol. 204 https://doi.org/10.1016/j.polymdegradstab.2022.110095	journal	October 2022
Embrittlement induced by oxidation in polyethylene: Role of initial bimodality Laot, R.; Le Gac, P. -Y.; Le Gall, M. Polymer Degradation and Stability, Vol. 230 https://doi.org/10.1016/j.polymdegradstab.2024.111025	journal	December 2024
A critical molar mass separating the ductile and brittle regimes as revealed by thermal oxidation in polypropylene Fayolle, B.; Audouin, L.; Verdu, J. Polymer, Vol. 45, Issue 12 https://doi.org/10.1016/j.polymer.2004.03.069	journal	May 2004
Cavitation during tensile deformation of high-density polyethylene Pawlak, Andrzej Polymer, Vol. 48, Issue 5 https://doi.org/10.1016/j.polymer.2006.12.054	journal	February 2007
Investigation of polyamide 11 embrittlement during oxidative degradation Okamba-Diogo, Octavie; Richaud, Emmanuel; Verdu, Jacques Polymer, Vol. 82 https://doi.org/10.1016/j.polymer.2015.11.025	journal	January 2016
Cavitation phenomenon and mechanical properties of partially disentangled polypropylene Pawlak, Andrzej; Krajenta, Justyna; Galeski, Andrzej Polymer, Vol. 151 https://doi.org/10.1016/j.polymer.2018.07.033	journal	August 2018
Photo-oxidation of semicrystalline polymers: Damage nucleation versus growth Cundiff, K. N.; Madi, Y.; Benzerga, A. A. Polymer, Vol. 188 https://doi.org/10.1016/j.polymer.2019.122090	journal	February 2020
Impact of stress triaxiality, strain rate, and temperature on the mechanical response and morphology of PVDF Hund, Jonas; Granum, Henrik Møgster; Olufsen, Sindre Nordmark Polymer Testing, Vol. 114 https://doi.org/10.1016/j.polymertesting.2022.107717	journal	October 2022
Cavitation during deformation of semicrystalline polymers Pawlak, Andrzej; Galeski, Andrzej; Rozanski, Artur Progress in Polymer Science, Vol. 39, Issue 5 https://doi.org/10.1016/j.progpolymsci.2013.10.007	journal	May 2014
Strain-induced multiscale structural evolutions of crystallized polymers: From fundamental studies to recent progresses Xu, Shanshan; Zhou, Jian; Pan, Pengju Progress in Polymer Science, Vol. 140 https://doi.org/10.1016/j.progpolymsci.2023.101676	journal	May 2023
A comparison of stress triaxiality and strain distributions in notched bar geometries as determined by Bridgman expressions and finite element analysis Jones, Michael; Hole, Matthew; Davies, Catrin Mair Procedia Structural Integrity, Vol. 28 https://doi.org/10.1016/j.prostr.2020.11.032	journal	January 2020
Strain Rate Dependence of Amorphous Phase Instability in Semicrystalline Polymers: Insights from the Scale of Lamellar Stacks Guo, Hang; Zhu, Jianhe; Li, Chengyan Macromolecules, Vol. 57, Issue 9 https://doi.org/10.1021/acs.macromol.4c00242	journal	April 2024
Deformation Instabilities and Cavitation in Plastic Deformation of Semicrystalline Polyethylene Bartczak, Zbigniew; Vozniak, Alina Macromolecules, Vol. 57, Issue 14 https://doi.org/10.1021/acs.macromol.4c00642	journal	July 2024
Voiding Mechanisms in Deformed Polyamide 6 Observed at the Nanometric Scale Selles, Nathan; Cloetens, Peter; Proudhon, Henry Macromolecules, Vol. 50, Issue 11 https://doi.org/10.1021/acs.macromol.7b00727	journal	May 2017
Changes in the morphology of bulk spherulitic nylon 6 due to plastic deformation Galeski, A.; Argon, A. S.; Cohen, Robert E. Macromolecules, Vol. 21, Issue 9 https://doi.org/10.1021/ma00187a021	journal	September 1988
New Insight on Initiation of Cavitation in Semicrystalline Polymers: In-Situ SAXS Measurements Humbert, S.; Lame, O.; Chenal, J. M. Macromolecules, Vol. 43, Issue 17 https://doi.org/10.1021/ma101042d	journal	July 2010
Effect of Multiaxial Stress State on Morphology and Spatial Distribution of Voids in Deformed Semicrystalline Polymer Assessed by X-ray Tomography Laiarinandrasana, Lucien; Morgeneyer, Thilo F.; Proudhon, Henry Macromolecules, Vol. 45, Issue 11 https://doi.org/10.1021/ma3005247	journal	May 2012
Polymer Weathering: Photo-Oxidation Feldman, D. Journal of Polymers and the Environment, Vol. 10, Issue 4, p. 163-173 https://doi.org/10.1023/A:1021148205366	journal	October 2002
Fiji: an open-source platform for biological-image analysis Schindelin, Johannes; Arganda-Carreras, Ignacio; Frise, Erwin Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2019	journal	June 2012
Stress–strain curves of metallic materials and post‐necking strain hardening characterization: A review Tu, Shengwen; Ren, Xiaobo; He, Jianying Fatigue & Fracture of Engineering Materials & Structures, Vol. 43, Issue 1 https://doi.org/10.1111/ffe.13134	journal	October 2019
Deformation and cavitation at the spherulite scale of an isotactic polypropylene Laiarinandrasana, Lucien; Klinkova, Olga; Ovalle, Cristian Journal of Theoretical, Computational and Applied Mechanics https://doi.org/10.46298/jtcam.11335	journal	September 2024

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36 MATERIALS SCIENCE
UV aging
cavitation
polyamide
synchrotron tomography
triaxiality

Photo-oxidation of semicrystalline polymers: Effect of stress triaxiality on ductility

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