Theoretically optimized hybrid magnetic

nanoparticle concentrations for functional

gradient nanocomposites
Cite as: AIP Advances 10, 105209 (2020); https://doi.org/10.1063/5.0023941
Submitted: 03 August 2020 . Accepted: 12 September 2020 . Published Online: 05 October 2020

Deshan Liang, Xiao Cui, Xingqiao Ma, Xiaoming Shi, Jing Wang, Hasnain Mehdi Jafri, Junsheng Wang,
Zhengzhi Wang, and Houbing Huang

COLLECTIONS

Paper published as part of the special topic on Chemical Physics, Energy, Fluids and Plasmas, Materials Science
and Mathematical Physics

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AIP Advances 10, 105209 (2020); https://doi.org/10.1063/5.0023941 10, 105209

© 2020 Author(s).
 AIP Advances ARTICLE scitation.org/journal/adv

Theoretically optimized hybrid magnetic

nanoparticle concentrations for functional
gradient nanocomposites
Cite as: AIP Advances 10, 105209 (2020); doi: 10.1063/5.0023941
Submitted: 3 August 2020 • Accepted: 12 September 2020 •
Published Online: 5 October 2020

Deshan Liang,1 Xiao Cui,1 Xingqiao Ma,1,a) Xiaoming Shi,2 Jing Wang,2 Hasnain Mehdi Jafri,2
Junsheng Wang, Zhengzhi Wang, and Houbing Huang2,b)
2 3

AFFILIATIONS
1
Department of Physics, University of Science and Technology Beijing, Beijing 100083, China
2
Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, China
3
Department of Engineering Mechanics, School of Civil Engineering, Wuhan University, Wuhan, Hubei 430072, China

a)
Email: xqma@sas.ustb.edu.cn
b)
Author to whom correspondence should be addressed: hbhuang@bit.edu.cn

ABSTRACT
Magnetically actuated functional gradient nanocomposites have widely been used for ultra-durable biomimetic interfaces and surfaces. How-
ever, the mechanical and thermal mismatches in integrated systems containing dissimilar materials or structures usually cause failures. By
modulating the concentration of magnetic particles, a suitable mechanical gradient morphology can be generated to match different integrated
systems. In this work, a new model is developed to describe magnetic particle motion under the magnetic field. Hybrid nano-reinforcements
with two different magnetic particle sizes and concentrations were employed to optimize the magnetic particle concentration gradient. It was
observed that the diversification of concentration distribution can be achieved by tuning the sizes and concentrations of nanoparticles. The
present study, therefore, contributes toward the understanding of the transport mechanism of magnetic-field-actuated functional gradient
nanocomposites and provides guidance for experiments to design ultra-durable biomimetic interfaces and surfaces.
© 2020 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0023941., s

I. INTRODUCTION wearable electronics,17,18 and other fields.19–23 However, problems

Magnetically actuated functional gradient nanocomposites
have been widely applied in ultra-durable biomimetic interfaces and
surfaces. For example, to improve resistance to contact damage and
layer delamination,1–3 the shell of a mollusk undergoes ∼40% grad-
ual changes between inter-crystalline soft organic layers and stiff
ceramic crystallites.4 It is a wonderful idea to mimic such processes
in artificial composites. Fabricating controllable functional gradient
nanocomposites (FGNCs) is a great achievement in mimicking the
gradient structure of nature. FGNCs can achieve better mechani-
cal properties5,6 by gradient distribution to satisfy a wide range of
industrial demands, including greater stiffness, super strength, and
fracture resistance.7–12 Therefore, it is widely used in the fields of
biomaterials,13–16 multilayer graphite nanocomposites, flexible and
exist in practical applications like hardness insufficiency in the coat-
ing industry24,25 and lower crack penetration in biomedical implants
and restorations,22 where most failures are caused by mechani-
cal/thermal mismatches in integrated systems containing dissimilar
materials or structures.
The concentration gradient of magnetic nanoparticles (NPs)
can be modulated under the external magnetic field, and magnet-
ically actuated FGNCs will get suitable mechanical properties to
enhance their hardness and toughness. Several schemes have been
applied to manipulate the nanoparticle distributions, for example,
using a micro-electro-magnetic matrix and a micro-electro-magnet
ring trap to control and manipulate magnetic NPs,26 using uniform
and non-uniform magnetic fields to control the motion of particles
to prepare magnetic-field-sensitive gel beads and monolith gels,27

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and using a self-assembly system with soft-magnetic hollow cylinder
template elements embedded in a nonmagnetic substrate to achieve
extraordinary control of particle motion.28 The directional motion
of uniformly small-sized magnetic NPs by a single cylindrical mag-
net has also been reported, but the maximum packing fraction of
particles was limited.29
In this paper, we studied the transport mechanism of differ-
ent sized core–shell particles (Fe3 O4 @SiO2 ). First, we calculated the
magnetic force and spatial concentration gradient distribution of
NPs (20 nm–100 nm). Later, we adopted hybrid particles (large and
small sizes) and simulated the spatial concentration distribution of
hybrid NPs. The results demonstrate that hybrid NPs can achieve an
optimum magnetic particle concentration gradient.
II. NUMERICAL METHODS
Redistributions of magnetic NPs in a fluid matrix under a
magnetic field can be simulated by the Brownian motion under a
magnetic field.30 This motion process is governed by several forces
including magnetic force, fluidic viscosity resistance, and thermal
fluctuation.31–33 In our model, we take magnetic force, fluidic vis-
cosity resistance, and thermodynamic fluctuating force into account.
The transport of NPs can be assumed as a Brownian motion pro-
the right side Ff (t) is the thermodynamic fluctuating force of the
magnetic NPs, and the second term Fη (t) is the viscous dragging
force.
For a magnetic nanoparticle submerged in a viscous fluid and
subjected to a gradient magnetic field, the magnetic force (Fm )
applied to the particle can be calculated as35
(χp − χf )Vp (B ⋅ ∇B)
Fm = , (2)
μ0
where χ p and χ f are the magnetic susceptibility of the magnetic
nanoparticle and the polymer matrix, respectively, V p is the volume
of the magnetic nanoparticle, B = μ0 H is the magnetic flux density
of the applied magnetic field, where μ0 is the permeability of the
free space and H is the applied magnetic field at the center of the
nanoparticle, and ∇ is the gradient operator.
The viscous force Fη (t) can be calculated by
dr
Fη (t) = −6πηRp , (3)
dt
where η is the viscous constant of the liquid and Rp is the radius of
the nanoparticle. The diffusion constant D can be expressed by the
kB T
Einstein relation D = 6πηR .
p

cess with the evolving particle positions predicted by Langevin’s In a system without damping, the fluctuating force component
equation,34 of a nanoparticle can be calculated by
d2 r d2 r
m = Ff (t) + Fη (t) + Fm (r), (1) Ff (t) = m , (4)
dt 2 dt 2
where m is the mass of the nanoparticle, r is the position of the par- where x is the displacement, t is the time, and m is the mass of a
ticle within the polymer matrix, and t is the time. The first term of nanoparticle. Besides,

FIG. 1. (a) Schematics of two magnets,

the nanopillar, and different sized NPs
and the right side is the magnetic field
distribution of two magnets, (b) magnetic
forces of different sized NPs, and (c)
NP concentration (20 nm–100 nm) as a
function of distance from the left of the
pillar.

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FIG. 2. [(a)–(d)] Spatial distributions and

concentration distributions for 20 nm and
40 nm, 20 nm and 60 nm, 20 nm and
80 nm, and 20 nm and 100 nm hybrid
NPs, respectively.

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⟨Ff (t)⟩ = 0, (5) We simulated the motion of 30 000 magnetic NPs in a pillar
sample and divided the pillar into 40 layers, and the magnetic forces
dr 2 on each magnetic nanoparticle within the polymer matrix were
⟨m( ) ⟩ = 3kB T, (6) obtained at every simulation step. For the micropillars considered,
dt
we adopted the elastic scattering boundary conditions.
where kB is the Boltzmann constant and T is the absolute tempera- As reported earlier,29,36 core–shell NPs (Fe3 O4 @SiO2 , ∼20 nm
ture. in diameter) can be dispersed in the polymer matrices under a

FIG. 3. [(a)–(c)] Spatial distributions and concentration distributions for 100 nm and 40 nm, 100 nm and 60 nm, and 100 nm and 80 nm hybrid NPs, respectively.

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© Author(s) 2020
 AIP Advances
magnetic field. However, these small particles have two disadvan-
tages. First, it requires strong magnetic field excitation and long
driving time to form the gradient due to the relatively low mag-
netic responsivity of small NPs. Second, the ultrahigh specific surface
areas limit their maximum packing fraction inside the matrix and
the magnitude of the mechanical gradient of the FGNCs.29 We have
made improvements to obtain a concentration gradient distribution
of NPs. First, we used two magnets instead of a single magnet to sig-
nificantly increase the magnetic force.37 Second, a combination of
hybrid NPs with different ratios was used to maximize the packing
fraction inside the polymer matrix. All the parameters were adopted
from our previous work of Refs. 36 and 38.
III. RESULTS
In the model, the distance between the two magnets is 1 cm, and
the distance from the pillar to the right magnet is 0.2 cm. In addition,
the pillar length is 40 μm, and the pillar diameter is 5 μm. Five differ-
ent sized NPs (20 nm–100 nm) are selected, as shown in Fig. 1(a). We
calculated the distribution of the magnetic field, which is shown at
the right of Fig. 1(a). The magnitudes of the magnetic force for NPs
are shown in Fig. 1(b). Since the pillar size is small compared with
the distance between two magnets, the magnetic force over the NPs
was approximated to be uniform. Figure 1(b) shows that the mag-
netic force increases with the particle radius. The large sized NP is
driven by a large magnetic force, while the small sized NP is driven
by a small magnetic force at the same position between two mag-
nets. We choose the concentration of NPs with 40 vol. % inside the
pillar. Under the driving of the magnetic force, the spatial concen-
tration distribution was calculated for different sized magnetic NPs,
as shown in Fig. 1(c). The NPs move to the right of the pillar under
the magnetic field. The concentration distribution of a large sized
NP (100 nm) has a high gradient under the same magnitude of the
magnetic field.
To deeply investigate the concentration distribution of NPs
under the magnetic field, we simulated 20 nm NPs and hybrid dif-
ferent sized NPs with an initial concentration of 20% for each size.
FIG. 4. (a) NP concentration as a function of distance from the sample left for 100 nm (20 vol. %) and 20 nm (5 vol. %, 10 vol. %, 15 vol. %, and 20 vol. %) and (b) NP
concentration as a function of distance from the sample left for 20 nm (20 vol. %) and 100 nm (5 vol. %, 10 vol. %, 15 vol. %, and 20 vol. %).
AIP Advances 10, 105209 (2020); doi: 10.1063/5.0023941
© Author(s) 2020
ARTICLE scitation.org/journal/adv
As shown in Fig. 2(a), we calculated the spatial distribution and the
concentration distribution of 40 nm and 20 nm NPs. According to
Fig. 1(c), the concentration of the right side is larger than that of the
left side for all different sized NPs. However, the right side concen-
tration of 20 nm NPs is lower than that of the left side, as shown in
Fig. 2(a), in the hybrid NPs. Since 40 nm NPs occupy the right side
space under the large magnetic force, the concentration of 20 nm
NPs in the right side, therefore, decreases. Different from the pre-
vious drift model, our model can simulate the space occupied by
NPs. Figures 2(b)–2(d) show the spatial distribution and the con-
centration distribution of (20 nm and 60 nm), (20 nm and 80 nm),
and (20 nm and 100 nm), respectively. Our model did not take into
account the interaction of the particles. The large and small sized
particles move to the right side with the same average velocity under
the driving of the magnetic field. Since the mass of the large sized
particle is larger than that of the small sized particle, the large sized
particle will have a larger inertial force. With the increase in the NP
radius, the concentration of larger NPs also increases. Therefore, the
large size NP will extrude the small size NP at the right side of the
sample.
As shown in Fig. 3(a), we calculated the spatial distribution and
the concentration distribution of 100 nm and 40 nm NPs. Since
100 nm NPs occupy the right side space under the large magnetic
force, the concentration of 40 nm NPs in the right side, therefore,
decreases. Figures 3(b) and 3(c) show the spatial distribution and
the concentration distribution of (100 nm and 60 nm) and (100 nm
and 80 nm), respectively. The large sized NPs extrude the small sized
NPs at the right side of the sample. It shows that 100 nm NPs squeeze
out the smaller size NPs at the right of the sample. In addition, with
the increase in the NP radius from 40 nm to 80 nm in the hybrid
particles, the concentration of 80 nm is higher than that of 40 nm on
the right side.
To optimize the concentration of NPs, we also investigate 20%
100 nm NPs mixing with 5%, 10%, 15%, and 20% 20 nm NPs. As
shown in Fig. 4(a), with the increase in the concentration of 20 nm
NPs, the concentration on the left of the sample increased accord-
ingly. In contrast, we simulate 20% 20 nm NPs mixing with 5%,
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5
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