Polymer-Grafted Nanoparticles

Cite as: J. Appl. Phys. 128, 030401 (2020); https://doi.org/10.1063/5.0019326

Submitted: 23 June 2020 . Accepted: 24 June 2020 . Published Online: 20 July 2020

Michael J. A. Hore , LaShanda T. J. Korley , and Sanat K. Kumar

COLLECTIONS

Paper published as part of the special topic on Polymer-Grafted Nanoparticles

Note: This paper is part of the Special Topic on Polymer-Grafted Nanoparticles.

J. Appl. Phys. 128, 030401 (2020); https://doi.org/10.1063/5.0019326 128, 030401

© 2020 Author(s).
 Journal of EDITORIAL scitation.org/journal/jap
Applied Physics

Polymer-Grafted Nanoparticles
Cite as: J. Appl. Phys. 128, 030401 (2020); doi: 10.1063/5.0019326
Submitted: 23 June 2020 · Accepted: 24 June 2020 · View Online Export Citation CrossMark
Published Online: 20 July 2020

Michael J. A. Hore,1,a) LaShanda T. J. Korley,2,b) and Sanat K. Kumar3,c)

AFFILIATIONS
1
Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44122, USA
2
Department of Materials Science and Engineering and Department of Chemical and Biomolecular Engineering,
University of Delaware, Newark, Delaware 19717, USA
3
Department of Chemical Engineering, Columbia University, New York, 10027, USA

Note: This paper is part of the Special Topic on Polymer-Grafted Nanoparticles.

a)
Author to whom correspondence should be addressed: hore@case.edu
b)
E-mail: lkorley@udel.edu
c)
E-mail: sk2794@columbia.edu

I. INTRODUCTION briefly review some of the fundamental concepts common to differ-

Polymer nanocomposites are an important class of materials. 1–5
They combine the many desirable physical properties of polymers,
such as their mechanical properties and ease of processing, with
functionalities provided by a nanoparticle component. The nanopar-
ticles can provide mechanical reinforcement, as well as impart
unique optical responses, enhanced electrical conductivities,
decreased gas permeability, and so on. To obtain these enhanced
physical properties from the nanoparticle component, the spatial dis-
persion of the nanoparticles (NPs) must be controlled—this fact has
now been well-appreciated and the focus of community work in the
last few decades.1–5 The limiting step in this context is that inorganic
NPs (typically hydrophilic) are immiscible with non-polar,
hydrocarbon-based polymers. A common approach to resolve this
difficulty is to attach polymer chains from the nanoparticle surface—
leading to “polymer-grafted” nanoparticles (PGNPs)—which have
surfactant-like behavior because hydrophilic and hydrophobic com-
ponents are chemically tethered to each other.6 However, PGNPs
have uses that go beyond traditional polymer nanocomposites, and
this class of nanoparticles can be broadly defined to include micellar
particles, single chain nanoparticles, and many others that are
covered in this Polymer-Grafted Nanoparticles Special Topic.2,5 In
this Guest Editorial, we will briefly review key fundamental concepts
related to PGNP properties and introduce the articles that comprise
the Special Topic. These articles cover (i) grafting strategies to
enhance dispersion, (ii) environmental tuning of PGNPs, (iii)
advances in PGNP characterization, and (iv) modeling efforts.
II. BACKGROUND
There is a wealth of information regarding PGNP properties
in the literature, including many reviews and perspectives. Here, we
ent types of PGNPs.
PGNPs include those with an inorganic core from which
polymer chains can be grown or attached. The inorganic core may
be SiO2, Ag, Au, CdSe, Fe3O4, graphene, clay, or many other mate-
rials. Using polymerization methods such as surface-initiated atom
transfer radical polymerization (SI-ATRP) or surface-initiated
reversible addition-fragmentation chain transfer polymerization
(SI-RAFT),7,8 these “grafting-from” techniques have the ability to
produce dense polymer brushes on the surface and can generate
complex brush configurations, such as ones containing a bimodal
distribution of molecular weights.9 An alternative approach to
“grafting-from” is to graft polymers to the surface of a nanoparticle
by taking advantage of polymer chains with terminal functional
groups. A common example is using thiol-terminated polymers to
graft to the surface of Au nanoparticles.10,11 The “grafting-to”
approach may be easier to accomplish experimentally but typically
results in lower grafting densities, especially for high molecular
weight polymers. Other types of PGNPs include those synthesized
via polymerization-induced self-assembly (PISA) of block copoly-
mers.12 In this process, polymers self-assemble in solution as poly-
merization proceeds, leading to an array of possible structures,
including spheres, vesicles, and worm-like particles. The particles
are not unlike those formed by surfactants in solution; in fact,
polymer chains can self-assemble in solution to form micellar
structures that behave like PGNPs in many ways.13 Recently, virus-
like particles have been synthesized and functionalized with a
polymer brush.14 Finally, nanoparticles can be synthesized by
crosslinking single chains into small, dense nanoparticles. Those
particles may contain a corona on the exterior—resembling a
PGNP—or may appear more solid-like, depending on the synthesis
conditions.15

J. Appl. Phys. 128, 030401 (2020); doi: 10.1063/5.0019326 128, 030401-1

Published under license by AIP Publishing.
 Journal of
Applied Physics
The structures of polymer brushes that result from grafting
chains to a surface depend on a range of factors, including grafting
density, polymer molecular weight, and interactions between the
chains and their environments.16 At low grafting densities, a brush
may not form and the conformation of the polymer chains is
similar to that of free chains. As grafting density increases, excluded
volume effects lead to stretched conformations.4 Polymer micelles
exhibit similar conformations in their coronas. Stretched chains
may exhibit slower relaxation dynamics, which can impact the
mechanical properties of nanocomposite materials.17–20 The
brush also influences nanoparticle organization within a material.
Autophobic dewetting is an entropic effect observed in systems in
which the chemical composition of the grafted chains is the same
as free, matrix chains. It affects nanoparticle dispersion, polymer dif-
fusion, and for plasmonic nanoparticles, optical properties of nano-
composite materials.2,3,21 As demonstrated in the Polymer-Grafted
Nanoparticles Special Topic, as well as several studies in the litera-
ture, if there are favorable interactions between a brush and its envi-
ronment, it becomes possible to significantly enhance dispersion
within a material or to spatially confine particles, such as in one
domain of an ordered block copolymer.22
Finally, numerous techniques exist for studying PGNPs on
both the experimental and theoretical ends of the spectrum. These
techniques include small-angle scattering for determining brush
structure,13,20,23,24 quasi-elastic scattering for following brush and
particle dynamics,19,20,25,26 and electron tomography for real space
imaging of grafting polymers when there is sufficient electron con-
trast.14,27 On the theoretical side, Monte Carlo simulations,
polymer field theories, and molecular dynamics techniques have
proven to be very successful, although many open challenges
remain.28 The Polymer-Grafted Nanoparticles Special Topic con-
tains several tutorials and research articles that expand on these
methods.
III. OVERVIEW OF TOPICS
A. Grafting strategies to enhance dispersion of PGNPs
Utilizing SI-ATRP as platform, Zhang et al.29 design poly
(methyl methacrylate) grafted-silicon nanoparticles and probe the
impact of reaction conditions on grafting architecture. Penaloza
and Seery describe a surface-initiated approach to the design of
polymer-tethered clay nanocomposites.30 By controlling and tuning
the architecture of the tethered polymer brushes on the clay
surface, the authors highlight a robust strategy to enhance disper-
sion in polymer nanocomposites. Extending grafting approaches to
understudied immiscible systems, Hickey et al.31 detail an innova-
tive in situ technique that balances enthalpic and entropic compo-
nents in the quest for well-dispersed polymer nanocomposites. To
apply these concepts to biomedicine, Ray and colleagues devise a
reverse micelle process to fabricate poly(acrylate) tethered-reduced
graphene oxide nanocomposites.32 This approach enables water sol-
ubility and enhances paramagnetic response. Aggregation of matrix-
free polymer grafted gold nanoparticles is examined as a function of
nanoparticle sphericity controlled via grafting density and polymer
chain molecular weight, and connections are drawn to its influence
on plasmonic behavior.33 Gogoi and Chowdhury utilize nanocompo-
site technology to combine polymer functionalization with layered
J. Appl. Phys. 128, 030401 (2020); doi: 10.1063/5.0019326
Published under license by AIP Publishing.
EDITORIAL scitation.org/journal/jap
nanohybrid materials to manufacture devices with enhanced resistive
memory performance due to synergistic behavior.34 Utilizing func-
tionalized silica nanoparticles, Rishi et al.35 investigate the dispersion
and specific interactions of elastomeric nanoparticles via spectro-
scopic, scattering, and modeling studies.
B. Environmental tuning of PGNPs
Block copolymer structures serve as scaffolds to tune the
assembled architecture of confined, polymer-grafted nanoparticles
in a self-consistent field theory investigation, revealing a rich
variety of PGNP morphologies.36 Solvent quality is also a handle to
control nanostructure in functionalized nanoparticles, leading to a
facile process to tailor morphology derived from a single starting
material.37 Perilla and co-workers38 describe zwitterionic grafted
silica nanoparticles with changes in hydrodynamic radius dictated
by pH, temperature, and ionic concentration, showcasing their
potential as therapeutic delivery vehicles. Domhoff and Davis
explore the interplay of substrate interactions on morphology and
ion transport in solvent-cast, silica/ionomer nanocomposite mem-
branes as a potential handle for flow battery design.39 An ice-
templating approach is used to fabricate microporous nanocompo-
site materials with mechanical response tuned by particle shape
and pH-responsive particle-matrix interactions.40
C. Advances in PGNP characterization
An in-depth tutorial of the use of quasi-elastic neutron scat-
tering spectroscopy to probe local and macroscopic dynamics in
polymer nanocomposites with a focus on spatial and temporal con-
siderations is included.41 Rose et al.42 present a tutorial on the fun-
damentals of high resolution optical microscopy applied to particle
tracking to correlate nanoscale dynamics in soft materials. Epoxy
curing provides a model system to showcase x-ray photon correla-
tion spectroscopy as a technique to explore curing kinetics via
nanoscale dynamics of filler particles.43 Colmenero et al.44 high-
light neutron scattering techniques as a viable strategy to investigate
structural heterogeneities in melts of intramolecularly crosslinked,
single chain nanoparticles, focusing on relaxation events at various
length scales. Rostom and Dadmum introduce a unique strategy to
measure nanoparticle diffusion in polymer nanocomposites, utiliz-
ing all-particle nanocomposites with tunability in nanoparticle soft-
ness to probe motion within the matrix.45 Geethu and colleagues
track percolation in and stability of microemulsions as a function
of hydrophobic chain length via dielectric spectroscopy and small-
angle neutron scattering.46
D. Modeling of PGNPs
Molecular dynamics simulation enables the examination of
different regimes of surface switching of mixed polyelectrolyte
brushes as a function of length and charge fraction of the arms,
strength of electrostatic interactions, and environmental condi-
tions.47 Langevin dynamics simulations are also employed to probe
polymer-grafted nanoparticles with constrained or unconstrained
soft polymer shells.48 The impact of polymer-grafted nanoparticles
with asymmetry in glass transition temperatures is examined using
128, 030401-2
 Journal of EDITORIAL scitation.org/journal/jap
Applied Physics

23
molecular simulations to understand the reinforcing effect in nano- M. J. A. Hore, J. Ford, K. Ohno, R. J. Composto, and B. Hammouda,
composites as it relates to dynamics.49 Macromolecules 46, 9341 (2013).
24
E. Buenning, J. Jestin, Y. Huang, B. C. Benicewicz, C. J. Durning, and
S. K. Kumar, ACS Macro Lett. 7, 1051 (2018).
ACKNOWLEDGMENTS 25
N. Jiang, M. K. Endoh, T. Koga, T. Masui, H. Kishimoto, M. Nagao,
The guest editors thank all of the authors who contributed S. K. Satija, and T. Taniguchi, ACS Macro Lett. 4, 838 (2015).
26
articles to this Special Topic of the Journal of Applied Physics. R. Poling-Skutvik, K. N. Olafson, S. Narayanan, L. Stingaciu, A. Faraone,
J. C. Conrad, and R. Krishnamoorti, Macromolecules 50, 7372 (2017).
27
S. Tang, T.-Y. Lo, J. M. Horton, C. Bao, P. Tang, F. Qiu, R.-M. Ho, B. Zhao,
REFERENCES
and L. Zhu, Macromolecules 46, 6575 (2013).
1
K. I. Winey and R. A. Vaia, MRS Bull 32, 314 (2007). 28
S. K. Kumar, V. Ganesan, and R. A. Riggleman, J. Chem. Phys. 147, 020901
2
S. K. Kumar, N. Jouault, B. Benicewicz, and T. Neely, Macromolecules 46, 3199 (2017).
(2013). 29
X. Xu, Y. Zou, J. He, Y. Zeng, C. Yu, and F. Zhang, J. Appl. Phys. 127, 115102
3
M. J. A. Hore and R. J. Composto, Macromolecules 47, 875 (2014). (2020).
4
M. J. A. Hore, Soft Matter 15, 1120 (2019). 30
D. P. Penaloza and T. A. P. Seery, J. Appl. Phys. 127, 164702 (2020).
5
S. K. Kumar, B. C. Benicewicz, R. A. Vaia, and K. I. Winey, Macromolecules 50, 31
J. A. LaNasa, V. M. Torres, and R. J. Hickey, J. Appl. Phys. 127, 134701
714 (2017). (2020).
6 32
P. Akcora, H. Liu, S. K. Kumar, J. Moll, Y. Li, B. C. Benicewicz, L. S. Schadler, E. S. Ganya, N. Soin, S. J. Moloi, J. A. McLaughlin, W. F. Pong, and S. C. Ray,
D. Acehan, A. Z. Panagiotopoulos, V. Pryamitsyn, V. Ganesan, J. Ilavsky, J. Appl. Phys. 127, 054302 (2020).
33
P. Thiyagarajan, R. H. Colby, and J. F. Douglas, Nat. Mater. 8, 354 (2009). Y. Zhou, L. Yan, T. Maji, G. Lévêque, M. Gkikas, and G. Fytas, J. Appl. Phys.
7
D. A. Savin, J. Pyun, G. D. Patterson, T. Kowalewski, and K. Matyjaszewski, 127, 074302 (2020).
J. Polym. Sci., Part B Polym. Phys. 40, 2667 (2002). 34
K. K. Gogoi and A. Chowdhury, J. Appl. Phys. 127, 065501 (2020).
8
C. Li, J. Han, C. Y. Ryu, and B. C. Benicewicz, Macromolecules 39, 3175 35
K. Rishi, L. Pallerla, G. Beaucage, and A. Tang, J. Appl. Phys. 127, 174702
(2006). (2020).
9
A. Rungta, B. Natarajan, T. Neely, D. Dukes, L. S. Schadler, and 36
S. Gupta and P. Chokshi, J. Appl. Phys. 127, 074901 (2020).
37
B. C. Benicewicz, Macromolecules 45, 9303 (2012). S. Venkataraman, G. Wei, K. P. Mineart, J. L. Hedrick, V. M. Prabhu, and
10
L. Meli and P. F. Green, ACS Nano 2, 1305 (2008). Y. Y. Yang, J. Appl. Phys. 127, 125104 (2020).
11
H. Yockell-Lelièvre, J. Desbiens, and A. M. Ritcey, Langmuir 23, 2843 (2007). 38
ÁA Beltrán-Osuna, J. L. Gómez-Ribelles, and J. E. Perilla, J. Appl. Phys. 127,
12
N. J. Warren and S. P. Armes, J. Am. Chem. Soc. 136, 10174 (2014). 135106 (2020).
13
J. S. Pedersen, I. W. Hamley, C. Y. Ryu, and T. P. Lodge, Macromolecules 33, 39
A. Domhoff and E. M. Davis, J. Appl. Phys. 127, 174701 (2020).
40
542 (2000). G. Kumaraswamy, K. Suresh, H. Lama, M. G. Basavaraj, and D. K. Satapathy,
14
P. W. Lee, S. A. Isarov, J. D. Wallat, S. K. Molugu, S. Shukla, J. E. P. Sun, “Ice templated nanocomposites containing rod-like hematite particles: Interplay
J. Zhang, Y. Zheng, M. L. Dougherty, D. Konkolewicz, P. L. Stewart, between particle anisotropy and particle-matrix interactions,” J. Appl. Phys.
N. F. Steinmetz, M. J. A. Hore, and J. K. Pokorski, J. Am. Chem. Soc. 139, 3312 (in press).
(2017). 41
R. Ashkar, J. Appl. Phys. 127, 151101 (2020).
15 42
E. Harth, B. V. Horn, V. Y. Lee, D. S. Germack, C. P. Gonzales, R. D. Miller, K. A. Rose, M. Molaei, M. J. Boyle, D. Lee, J. C. Crocker, and R. J. Composto,
and C. J. Hawker, J. Am. Chem. Soc. 124, 8653 (2002). J. Appl. Phys. 127, 191101 (2020).
16 43
D. Dukes, Y. Li, S. Lewis, B. Benicewicz, L. Schadler, and S. K. Kumar, B. M. Yavitt, D. Salatto, Z. Huang, Y. T. Koga, M. K. Endoh, L. Wiegart,
Macromolecules 43, 1564 (2010). S. Poeller, S. Petrash, and T. Koga, J. Appl. Phys. 127, 114701 (2020).
44
17
S. A. Kim, R. Mangal, and L. A. Archer, Macromolecules 48, 6280 (2015). A. Arbe, J. Rubio, P. Malo de Molina, J. Maiz, J. A. Pomposo, P. Fouquet,
18
D. Kim, S. Srivastava, S. Narayanan, and L. A. Archer, Soft Matter 8, 10813 S. Prevost, F. Juranyi, M. Khaneft, and J. Colmenero, J. Appl. Phys. 127, 044305
(2012). (2020).
19
X. Frielinghaus, M. Brodeck, O. Holderer, and H. Frielinghaus, Langmuir 26, 45
S. Rostom and M. D. Dadmun, J. Appl. Phys. 127, 074303 (2020).
17444 (2010).
46
P. M. Geethu, V. K. Aswal, and D. K. Satapathy, J. Appl. Phys. 127, 224701
20
Y. Wei, Y. Xu, A. Faraone, and M. J. A. Hore, ACS Macro Lett. 7, 699 (2020).
(2018). 47
S. Wang and C. Tong, J. Appl. Phys. 127, 074301 (2020).
21 48
J. Choi, M. J. A. Hore, N. Clarke, K. I. Winey, and R. J. Composto, M. S. Marques, T. P. O. Nogueira, R. F. Dillenburg, M. C. Barbosa, and
Macromolecules 47, 2404 (2014). J. R. Bordin, J. Appl. Phys. 127, 054701 (2020).
22 49
S. Sanwaria, A. Horechyy, D. Wolf, C.-Y. Chu, H.-L. Chen, P. Formanek, W. Peng, R. Ranganathan, P. Keblinski, P. Akcora, and R. Ozisik, J. Appl.
M. Stamm, R. Srivastava, and B. Nandan, Angew. Chem., Int. Ed. 53, 9090 (2014). Phys. 126, 195102 (2019).

J. Appl. Phys. 128, 030401 (2020); doi: 10.1063/5.0019326 128, 030401-3

Published under license by AIP Publishing.