DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Materials by Design for Stiff and Tough Hairy Nanoparticle Assemblies

Abstract

We report matrix-free polymer-grafted nanocrystals, called assembled hairy nanoparticles (aHNPs), can significantly enhance the thermomechanical performance of nanocomposites by overcoming nanoparticle dispersion challenges and achieving stronger interfacial interactions through grafted polymer chains. However, effective strategies to improve both the mechanical stiffness and toughness of aHNPs are lacking given the general conflicting nature of these two properties and the large number of molecular parameters involved in the design of aHNPs. Here, we propose a computational framework that combines multiresponse Gaussian process metamodeling and coarse-grained molecular dynamics simulations to establish design strategies for achieving optimal mechanical properties of aHNPs within a parametric space. Taking poly(methyl methacrylate) grafted to high-aspect-ratio cellulose nanocrystals as a model nanocomposite, our multiobjective design optimization framework reveals that the polymer chain length and grafting density are the main influencing factors governing the mechanical properties of aHNPs, in comparison to the nanoparticle size and the polymer–nanoparticle interfacial interactions. In particular, the Pareto frontier, that marks the upper bound of mechanical properties within the design parameter space, can be achieved when the weight percentage of nanoparticles is above around 60% and the grafted chains exceed the critical length scale governing transition into the semidilute brush regime. We show that theoreticalmore » scaling relationships derived from the Daoud–Cotton model capture the dependence of the critical length scale on graft density and nanoparticle size. Lastly, our established modeling framework provides valuable insights into the mechanical behavior of these hairy nanoparticle assemblies at the molecular level and allows us to establish guidelines for nanocomposite design.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States); Northern Illinois Univ., DeKalb, IL (United States)
  3. North Dakota State Univ., Fargo, ND (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Ford Motor Company, Detroit, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1504739
Grant/Contract Number:  
EE0006867
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 8; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 42 ENGINEERING; assembled hairy nanoparticles; coarse-grained molecular dynamics; mechanical properties; multiresponse Gaussian process modeling; Pareto frontier

Citation Formats

Hansoge, Nitin K., Huang, Tianyu, Sinko, Robert, Xia, Wenjie, Chen, Wei, and Keten, Sinan. Materials by Design for Stiff and Tough Hairy Nanoparticle Assemblies. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b02454.
Hansoge, Nitin K., Huang, Tianyu, Sinko, Robert, Xia, Wenjie, Chen, Wei, & Keten, Sinan. Materials by Design for Stiff and Tough Hairy Nanoparticle Assemblies. United States. https://doi.org/10.1021/acsnano.8b02454
Hansoge, Nitin K., Huang, Tianyu, Sinko, Robert, Xia, Wenjie, Chen, Wei, and Keten, Sinan. Thu . "Materials by Design for Stiff and Tough Hairy Nanoparticle Assemblies". United States. https://doi.org/10.1021/acsnano.8b02454. https://www.osti.gov/servlets/purl/1504739.
@article{osti_1504739,
title = {Materials by Design for Stiff and Tough Hairy Nanoparticle Assemblies},
author = {Hansoge, Nitin K. and Huang, Tianyu and Sinko, Robert and Xia, Wenjie and Chen, Wei and Keten, Sinan},
abstractNote = {We report matrix-free polymer-grafted nanocrystals, called assembled hairy nanoparticles (aHNPs), can significantly enhance the thermomechanical performance of nanocomposites by overcoming nanoparticle dispersion challenges and achieving stronger interfacial interactions through grafted polymer chains. However, effective strategies to improve both the mechanical stiffness and toughness of aHNPs are lacking given the general conflicting nature of these two properties and the large number of molecular parameters involved in the design of aHNPs. Here, we propose a computational framework that combines multiresponse Gaussian process metamodeling and coarse-grained molecular dynamics simulations to establish design strategies for achieving optimal mechanical properties of aHNPs within a parametric space. Taking poly(methyl methacrylate) grafted to high-aspect-ratio cellulose nanocrystals as a model nanocomposite, our multiobjective design optimization framework reveals that the polymer chain length and grafting density are the main influencing factors governing the mechanical properties of aHNPs, in comparison to the nanoparticle size and the polymer–nanoparticle interfacial interactions. In particular, the Pareto frontier, that marks the upper bound of mechanical properties within the design parameter space, can be achieved when the weight percentage of nanoparticles is above around 60% and the grafted chains exceed the critical length scale governing transition into the semidilute brush regime. We show that theoretical scaling relationships derived from the Daoud–Cotton model capture the dependence of the critical length scale on graft density and nanoparticle size. Lastly, our established modeling framework provides valuable insights into the mechanical behavior of these hairy nanoparticle assemblies at the molecular level and allows us to establish guidelines for nanocomposite design.},
doi = {10.1021/acsnano.8b02454},
journal = {ACS Nano},
number = 8,
volume = 12,
place = {United States},
year = {Thu Jul 05 00:00:00 EDT 2018},
month = {Thu Jul 05 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Structural and mechanical properties of polymer nanocomposites
journal, August 2006


The Halpin-Tsai equations: A review
journal, May 1976

  • Affdl, J. C. Halpin; Kardos, J. L.
  • Polymer Engineering and Science, Vol. 16, Issue 5
  • DOI: 10.1002/pen.760160512

Toughening fragile matter: mechanical properties of particle solids assembled from polymer-grafted hybrid particles synthesized by ATRP
journal, January 2012

  • Choi, Jihoon; Hui, Chin Ming; Pietrasik, Joanna
  • Soft Matter, Vol. 8, Issue 15
  • DOI: 10.1039/c2sm06915f

Mechanical Properties of Thin Glassy Polymer Films Filled with Spherical Polymer-Grafted Nanoparticles
journal, July 2012

  • Maillard, Damien; Kumar, Sanat K.; Fragneaud, Benjamin
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301792g

Polymer Nanocomposites Containing Carbon Nanotubes
journal, August 2006

  • Moniruzzaman, Mohammad; Winey, Karen I.
  • Macromolecules, Vol. 39, Issue 16
  • DOI: 10.1021/ma060733p

Star shaped polymers : a model for the conformation and its concentration dependence
journal, January 1982


Structural diversity in binary superlattices self-assembled from polymer-grafted nanocrystals
journal, December 2015

  • Ye, Xingchen; Zhu, Chenhui; Ercius, Peter
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms10052

Structure and transport properties of polymer grafted nanoparticles
journal, November 2011

  • Goyal, Sushmit; Escobedo, Fernando A.
  • The Journal of Chemical Physics, Vol. 135, Issue 18
  • DOI: 10.1063/1.3657831

Perspective: Evolutionary design of granular media and block copolymer patterns
journal, April 2016

  • Jaeger, Heinrich M.; de Pablo, Juan J.
  • APL Materials, Vol. 4, Issue 5
  • DOI: 10.1063/1.4948270

Cross-Validation
book, January 2009


Graphene-based polymer nanocomposites
journal, January 2011


Strategies for Dispersing Nanoparticles in Polymers
journal, April 2007


Optimal Length Scales Emerging from Shear Load Transfer in Natural Materials: Application to Carbon-Based Nanocomposite Design
journal, February 2012

  • Wei, Xiaoding; Naraghi, Mohammad; Espinosa, Horacio D.
  • ACS Nano, Vol. 6, Issue 3
  • DOI: 10.1021/nn204506d

Processing fragile matter: effect of polymer graft modification on the mechanical properties and processibility of (nano-) particulate solids
journal, January 2016

  • Schmitt, Michael; Choi, Jihoon; Min Hui, Chin
  • Soft Matter, Vol. 12, Issue 15
  • DOI: 10.1039/C6SM00095A

Tuning Glass Transition in Polymer Nanocomposites with Functionalized Cellulose Nanocrystals through Nanoconfinement
journal, September 2015


Effect of Nanoparticle Mobility on Toughness of Polymer Nanocomposites
journal, March 2005


Molecular Mechanisms of Failure in Polymer Nanocomposites
journal, July 2002


Small but strong: A review of the mechanical properties of carbon nanotube–polymer composites
journal, August 2006


Thermomechanically Consistent and Temperature Transferable Coarse-Graining of Atactic Polystyrene
journal, April 2015


Physical aging and glass transition of hairy nanoparticle assemblies
journal, October 2015

  • Koerner, Hilmar; Opsitnick, Elizabeth; Grabowski, Christopher A.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 2
  • DOI: 10.1002/polb.23931

Energy Renormalization for Coarse-Graining the Dynamics of a Model Glass-Forming Liquid
journal, February 2018

  • Xia, Wenjie; Song, Jake; Hansoge, Nitin K.
  • The Journal of Physical Chemistry B, Vol. 122, Issue 6
  • DOI: 10.1021/acs.jpcb.8b00321

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Cracks and Crazes: On Calculating the Macroscopic Fracture Energy of Glassy Polymers from Molecular Simulations
journal, September 2002


Systematic Method for Thermomechanically Consistent Coarse-Graining: A Universal Model for Methacrylate-Based Polymers
journal, May 2014

  • Hsu, David D.; Xia, Wenjie; Arturo, Steven G.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 6
  • DOI: 10.1021/ct500080h

Review: current international research into cellulose nanofibres and nanocomposites
journal, January 2010


Understanding the Interfacial Mechanical Response of Nanoscale Polymer Thin Films via Nanoindentation
journal, May 2016


Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals
journal, February 2017

  • Gu, X. Wendy; Ye, Xingchen; Koshy, David M.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 11
  • DOI: 10.1073/pnas.1618508114

Gaussian process emulation of dynamic computer codes
journal, June 2009


A Descriptor-Based Design Methodology for Developing Heterogeneous Microstructural Materials System
journal, March 2014

  • Xu, Hongyi; Li, Yang; Brinson, Catherine
  • Journal of Mechanical Design, Vol. 136, Issue 5
  • DOI: 10.1115/1.4026649

Polymer-Grafted Cellulose Nanocrystals as pH-Responsive Reversible Flocculants
journal, August 2013

  • Kan, Kevin H. M.; Li, Jian; Wijesekera, Kushlani
  • Biomacromolecules, Vol. 14, Issue 9
  • DOI: 10.1021/bm400752k

Kriging Models for Global Approximation in Simulation-Based Multidisciplinary Design Optimization
journal, December 2001

  • Simpson, Timothy W.; Mauery, Timothy M.; Korte, John J.
  • AIAA Journal, Vol. 39, Issue 12
  • DOI: 10.2514/2.1234

Molecular simulation study of self-assembly of tethered V-shaped nanoparticles
journal, December 2008

  • Nguyen, Trung Dac; Zhang, Zhenli; Glotzer, Sharon C.
  • The Journal of Chemical Physics, Vol. 129, Issue 24
  • DOI: 10.1063/1.3025918

Survey of modeling and optimization strategies to solve high-dimensional design problems with computationally-expensive black-box functions
journal, August 2009

  • Shan, Songqing; Wang, G. Gary
  • Structural and Multidisciplinary Optimization, Vol. 41, Issue 2
  • DOI: 10.1007/s00158-009-0420-2

Flexible Particle Array Structures by Controlling Polymer Graft Architecture
journal, September 2010

  • Choi, Jihoon; Dong, Hongchen; Matyjaszewski, Krzysztof
  • Journal of the American Chemical Society, Vol. 132, Issue 36
  • DOI: 10.1021/ja105189s

Miscanthus Giganteus: A commercially viable sustainable source of cellulose nanocrystals
journal, January 2017


Preparation, properties and applications of polysaccharide nanocrystals in advanced functional nanomaterials: a review
journal, January 2012

  • Lin, Ning; Huang, Jin; Dufresne, Alain
  • Nanoscale, Vol. 4, Issue 11
  • DOI: 10.1039/c2nr30260h

Fracture toughness of calcium–silicate–hydrate from molecular dynamics simulations
journal, July 2015


On the use of nanocellulose as reinforcement in polymer matrix composites
journal, December 2014


Global sensitivity indices for nonlinear mathematical models and their Monte Carlo estimates
journal, February 2001


Highly Transparent and Toughened Poly(methyl methacrylate) Nanocomposite Films Containing Networks of Cellulose Nanofibrils
journal, November 2015

  • Dong, Hong; Sliozberg, Yelena R.; Snyder, James F.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 45
  • DOI: 10.1021/acsami.5b08317

Conformational Transitions of Spherical Polymer Brushes: Synthesis, Characterization, and Theory
journal, February 2010

  • Dukes, Douglas; Li, Yu; Lewis, Sarah
  • Macromolecules, Vol. 43, Issue 3
  • DOI: 10.1021/ma901228t

Review article: Polymer-matrix Nanocomposites, Processing, Manufacturing, and Application: An Overview
journal, January 2006

  • Hussain, Farzana; Hojjati, Mehdi; Okamoto, Masami
  • Journal of Composite Materials, Vol. 40, Issue 17
  • DOI: 10.1177/0021998306067321

Nanoemulsions and Nanolatexes Stabilized by Hydrophobically Functionalized Cellulose Nanocrystals
journal, August 2017


Review of Metamodeling Techniques in Support of Engineering Design Optimization
journal, May 2006

  • Wang, G. Gary; Shan, S.
  • Journal of Mechanical Design, Vol. 129, Issue 4
  • DOI: 10.1115/1.2429697

Current issues in research on structure–property relationships in polymer nanocomposites
journal, July 2010


Polymer-Grafted-Nanoparticles Nanocomposites: Dispersion, Grafted Chain Conformation, and Rheological Behavior
journal, January 2011

  • Chevigny, Chloé; Dalmas, Florent; Di Cola, Emanuela
  • Macromolecules, Vol. 44, Issue 1
  • DOI: 10.1021/ma101332s

Polylactic acid/polyurethane blend reinforced with cellulose nanocrystals with semi-interpenetrating polymer network (S-IPN) structure
journal, January 2017


Use of Kriging Models to Approximate Deterministic Computer Models
journal, April 2005

  • Martin, Jay D.; Simpson, Timothy W.
  • AIAA Journal, Vol. 43, Issue 4
  • DOI: 10.2514/1.8650

Performance of Dielectric Nanocomposites: Matrix-Free, Hairy Nanoparticle Assemblies and Amorphous Polymer–Nanoparticle Blends
journal, November 2014

  • Grabowski, Christopher A.; Koerner, Hilmar; Meth, Jeffrey S.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 23
  • DOI: 10.1021/am506521r

Effect of Polymer-Graft Modification on the Order Formation in Particle Assembly Structures
journal, May 2013

  • Choi, Jihoon; Hui, Chin Ming; Schmitt, Michael
  • Langmuir, Vol. 29, Issue 21
  • DOI: 10.1021/la4004406

Neutron Crystallography, Molecular Dynamics, and Quantum Mechanics Studies of the Nature of Hydrogen Bonding in Cellulose I β
journal, November 2008

  • Nishiyama, Yoshiharu; Johnson, Glenn P.; French, Alfred D.
  • Biomacromolecules, Vol. 9, Issue 11
  • DOI: 10.1021/bm800726v

Poly(methyl methacrylate)-grafted cellulose nanocrystals: One-step synthesis, nanocomposite preparation, and characterization
journal, March 2016

  • Kedzior, Stephanie A.; Graham, Lexa; Moorlag, Carolyn
  • The Canadian Journal of Chemical Engineering, Vol. 94, Issue 5
  • DOI: 10.1002/cjce.22456

Functionalized graphene sheets for polymer nanocomposites
journal, May 2008

  • Ramanathan, T.; Abdala, A. A.; Stankovich, S.
  • Nature Nanotechnology, Vol. 3, Issue 6, p. 327-331
  • DOI: 10.1038/nnano.2008.96

Critical length scales and strain localization govern the mechanical performance of multi-layer graphene assemblies
journal, January 2016

  • Xia, Wenjie; Ruiz, Luis; Pugno, Nicola M.
  • Nanoscale, Vol. 8, Issue 12
  • DOI: 10.1039/C5NR08488A

Predicting the Macroscopic Fracture Energy of Epoxy Resins from Atomistic Molecular Simulations
journal, December 2016


Glassy and Elastomeric Polyurethanes Filled with Nano-Silica Particles
journal, August 2000


Energy-Renormalization for Achieving Temperature Transferable Coarse-Graining of Polymer Dynamics
journal, October 2017


Perspective: NanoMine: A material genome approach for polymer nanocomposites analysis and design
journal, March 2016

  • Zhao, He; Li, Xiaolin; Zhang, Yichi
  • APL Materials, Vol. 4, Issue 5
  • DOI: 10.1063/1.4943679

Cellulose Nanocrystals Grafted with Polystyrene Chains through Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP)
journal, July 2009

  • Morandi, Gaelle; Heath, Lindy; Thielemans, Wim
  • Langmuir, Vol. 25, Issue 14
  • DOI: 10.1021/la900452a

Green and Efficient Synthesis of Dispersible Cellulose Nanocrystals in Biobased Polyesters for Engineering Applications
journal, April 2016

  • Spinella, Stephen; Samuel, Cédric; Raquez, Jean-Marie
  • ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 5
  • DOI: 10.1021/acssuschemeng.5b01611

An efficient algorithm for constructing optimal design of computer experiments
journal, September 2005

  • Jin, Ruichen; Chen, Wei; Sudjianto, Agus
  • Journal of Statistical Planning and Inference, Vol. 134, Issue 1
  • DOI: 10.1016/j.jspi.2004.02.014

Hairy nanoparticle assemblies as one-component functional polymer nanocomposites: opportunities and challenges
journal, March 2013

  • Fernandes, Nikhil J.; Koerner, Hilmar; Giannelis, Emmanuel P.
  • MRS Communications, Vol. 3, Issue 1
  • DOI: 10.1557/mrc.2013.9

A comparative study of metamodeling methods for multiobjective crashworthiness optimization
journal, September 2005


Metamodel based design optimization approach in promoting the performance of proton exchange membrane fuel cells
journal, November 2011


Polymer Nanocomposites
journal, April 2007


The role of cellulose nanocrystals in the improvement of the shape-memory properties of castor oil-based segmented thermoplastic polyurethanes
journal, February 2014


Viscoelastic Properties of Poly(methyl methacrylates) Prepared by Anionic Polymerization
journal, July 1970

  • Masuda, Toshiro; Kitagawa, Keishi; Onogi, Shigeharu
  • Polymer Journal, Vol. 1, Issue 4
  • DOI: 10.1295/polymj.1.418

A Review of the Properties and Applications of Poly (Methyl Methacrylate) (PMMA)
journal, June 2015


Leveraging the nugget parameter for efficient Gaussian process modeling
journal, February 2018

  • Bostanabad, Ramin; Kearney, Tucker; Tao, Siyu
  • International Journal for Numerical Methods in Engineering, Vol. 114, Issue 5
  • DOI: 10.1002/nme.5751

Cellulose nanomaterial reinforced polymer nanocomposites
journal, May 2017


Cellulose nanocrystals: synthesis, functional properties, and applications
journal, November 2015

  • George, Johnsy; S. N., Sabapathi
  • Nanotechnology, Science and Applications
  • DOI: 10.2147/NSA.S64386

Nanoparticle Polymer Composites: Where Two Small Worlds Meet
journal, November 2006

  • Balazs, A. C.; Emrick, T.; Russell, T. P.
  • Science, Vol. 314, Issue 5802, p. 1107-1110
  • DOI: 10.1126/science.1130557

Reinforcement of Optically Healable Supramolecular Polymers with Cellulose Nanocrystals
journal, December 2013

  • Coulibaly, Souleymane; Roulin, Anita; Balog, Sandor
  • Macromolecules, Vol. 47, Issue 1
  • DOI: 10.1021/ma402143c

Polymers end-grafted onto a cylindrical surface
journal, May 1991


Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications
journal, June 2010

  • Habibi, Youssef; Lucia, Lucian A.; Rojas, Orlando J.
  • Chemical Reviews, Vol. 110, Issue 6
  • DOI: 10.1021/cr900339w

Multi-Objective Decision Making of a Simplified Car Body Shape Towards Optimum Aerodynamic Performance
conference, August 2017

  • Song, Kisun; Choo, Kyung Hak; Kim, Jung-Hyun
  • Volume 2B: 43rd Design Automation Conference
  • DOI: 10.1115/DETC2017-67234

Works referencing / citing this record:

Disentangling the Role of Chain Conformation on the Mechanics of Polymer Tethered Particle Materials
journal, March 2019


Nanoparticles shape-specific emergent behaviour on liquid crystal droplets
journal, January 2020

  • Sumer, Zeynep; Striolo, Alberto
  • Molecular Systems Design & Engineering, Vol. 5, Issue 2
  • DOI: 10.1039/c9me00153k

Machine learning for composite materials
journal, March 2019


Mechanics of Strong and Tough Cellulose Nanopaper
journal, July 2019

  • Meng, Qinghua; Wang, Tie Jun
  • Applied Mechanics Reviews, Vol. 71, Issue 4
  • DOI: 10.1115/1.4044018

The interfacial zone in thin polymer films and around nanoparticles in polymer nanocomposites
journal, September 2019

  • Zhang, Wengang; Emamy, Hamed; Pazmiño Betancourt, Beatriz A.
  • The Journal of Chemical Physics, Vol. 151, Issue 12
  • DOI: 10.1063/1.5119269

Effect of Constituent Materials on Composite Performance: Exploring Design Strategies via Machine Learning
journal, April 2019