polymers

Review
Magnetic Polymer Composite Particles: Design
and Magnetorheology
Qi Lu 1,2 , Kisuk Choi 3 , Jae-Do Nam 3 and Hyoung Jin Choi 1,2, *

1 Department of Polymer Science and Engineering, Inha University, Incheon 22212, Korea; 22192255@inha.edu
2 Program of Environmental and Polymer Engineering, Inha University, Incheon 22212, Korea
3 Department of Polymer Science and Engineering, Sungkyunkwan University, Suwon 16419, Korea;
kisuk929@skku.edu (K.C.); jdnam@skku.edu (J.-D.N.)
* Correspondence: hjchoi@inha.ac.kr; Tel.: +82-32-860-7486

Abstract: As a family of smart functional hybrid materials, magnetic polymer composite particles
have attracted considerable attention owing to their outstanding magnetism, dispersion stability,
and fine biocompatibility. This review covers their magnetorheological properties, namely, flow
curve, yield stress, and viscoelastic behavior, along with their synthesis. Preparation methods
and characteristics of different types of magnetic composite particles are presented. Apart from
the research progress in magnetic polymer composite synthesis, we also discuss prospects of this
promising research field.

Keywords: magnetic polymer composite; magnetorheological; smart fluid

1. Introduction



Over the past few decades, the development of hybrid nanocomposite particles with


potential applications in multidimensional fields has led to the observation of spectacular
Citation: Lu, Q.; Choi, K.; Nam, J.-D.; new phenomena. Among the many nanomaterials used in industrial, environmental, and
Choi, H.J. Magnetic Polymer Composite biomedical applications, magnetic nanocomposite particles have attracted considerable
Particles: Design and Magnetorheology. attention because of their immanent magnetic properties. These composites are of poten-
Polymers 2021, 13, 512. https://
tial use as anticancer materials, magnetic resonance imaging [1,2], magnetic recoverable
doi.org/10.3390/polym13040512
catalysts [3], hyperthermia treatment [4–6], bio-separation [7], drug release agents [8,9],
and magnetorheological (MR) materials. However, the inherent instability of magnetic
Academic Editor: Elena Kramarenko
nanoparticle dispersions in a continuous phase over a long time is an urgent problem that
Received: 11 January 2021
should be addressed for facilitating the use of magnetic nanocomposite particles in various
Accepted: 1 February 2021
other applications. To minimize the energy generated by their large surface-volume ratio,
Published: 8 February 2021
magnetic nanoparticles tend to form aggregates. Furthermore, since pristine magnetic
metal nanoparticles are highly reactive in air and easily oxidized, they could lose their
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
magnetic properties as time goes. Therefore, from the perspective of their applications, it is
published maps and institutional affil-
of vital importance to develop protection strategies to stabilize bare magnetic particles and
iations.
prevent their degradation during or after synthesis.
The synthesis of hybrid materials encapsulated in a polymer matrix has provided
new possibilities for the scientific manufacture of solid-particle-forming materials. Specifi-
cally, it is important to maintain the long-term dispersion stability of magnetic polymer
nanoparticles, without agglomeration and precipitation. This is particularly important for
Copyright: © 2021 by the authors.
the synthesis of magnetic polymer nanoparticles from pure metals that are highly sensitive
Licensee MDPI, Basel, Switzerland.
This article is an open access article
to air, such as iron, cobalt, nickel, and their alloys. Consequently, among magnetic polymer
distributed under the terms and
composites, iron oxides or iron-oxide-based materials are of considerable research interest,
conditions of the Creative Commons
since they are more stable and easy to prepare [10–15]. On the other hand, studies have
Attribution (CC BY) license (https:// proposed the use of inorganic materials and polymers as carriers of magnetic composite
creativecommons.org/licenses/by/ materials since these composite materials can help modify the properties of the carriers for
4.0/). specific applications [16,17]. The fabrication of magnetic polymer particles can be divided

Polymers 2021, 13, 512. https://doi.org/10.3390/polym13040512 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 512 2 of 20

into three categories, which are described in the next section. Generally, encapsulating
magnetic particles in a polymer can inhibit not only iron leakage but also iron leakage from
oxidized magnetite, resulting in better colloidal stability, increased magnetite content, and
the formation of several ideal functional groups on the surface of the particles.
Actively tunable MR fluids consist of Brownian-motion-sustained nano- or microscale
soft magnetic particles [18–20] suspended in nonmagnetic liquids such as mineral oil, natu-
ral or mineral fatty acids, silicone oil paraffin, hydrocarbon oil, and silicone oil. Moreover,
various additives, such as dispersion stabilizers and surfactants can also be added to MR
fluids to prevent gravity sedimentation and enhance stable particle dispersion, increase
lubricity, and tune the medium viscosity [21–25]. When an external magnetic field field
strength (H) is applied, the yield stress and shear viscosity of MR fluids increase by sev-
eral orders of magnitude, and the MR fluids transform from a fluid-like to a solid-like
phase [26–29]. Under an external magnetic field, randomly dispersed free-moving particles,
which are aligned in the external magnetic field direction, in the fluids become polarized
and connect to neighboring particles to form aggregate fibril-like chain structures [30,31].
Both shear viscosity and elastic modulus of the MR fluids increase sharply, and they can be
controlled by adjusting the magnetic field strength. All these characteristics are closely re-
lated to the formulation of the MR fluids such as the magnetism, shape, and size of the MR
particles and the medium oil viscosity [32,33]. Similar behavior is shown by MR gels and
MR elastomers when the fluid medium is replaced with gels and elastomers, respectively.
Since their mechanical and rheological characteristics can be accurately controlled, they
have been adopted in various engineering systems such as vehicle suspensions, haptic
devices [34], dampers, power steering pumps, cancer therapeutic procedures, and drug
delivery systems. This review covers recent progress in the search for smart magnetic
polymer particles with improved dispersion stability and various analyses of their MR
characteristics. On the other hand, the electrical analog of the MR fluid, namely, the
electrorheological (ER) fluid based on electro-responsive particles, such as conducting poly-
mers and inorganic particles dispersed in a nonconducting liquid, exhibits a similar chain
formation mechanism involving the dispersed particles under an applied electric field [35].

2. Magnetic Polymer Materials

Magnetic particles generally refer to particles containing iron-, cobalt-, and nickel-
based ferromagnetic elements, alloys, oxides, or composite structures. Among different
types of magnetic materials, paramagnetic materials have a magnetization proportional to
the external H and positive susceptibility, while antimagnetic materials also have a magne-
tization proportional to the external H but have negative susceptibility. The magnetization
of ferromagnetic materials initially increases significantly with H and later saturates when
H reaches a certain value. Furthermore, soft magnetic particles are an important subclass
of magnetic materials because of their unique importance in energy applications such as in
motors, transformers, and sensors. The term “soft” is related to the intrinsic coercivity (Hco ).
The threshold used to characterize a material as soft is arbitrary: soft magnetic materials are
defined as magnetic materials with Hco ≤ 400–1000 A m−1 [36,37]. Generally soft magnetic
particles are observed in materials with a cubic crystalline structure; examples are Fe, Ni,
Co, Fe–Ni, Fe–Co, and metal oxides such as MFe2 O4 (where M is a divalent metal) [38].
The selection of a polymer matrix for magnetic polymer composite particles is based
on the intended use of the composite particles and the choice is either commodity plastics
(e.g., polystyrene (PS), polymethyl methacrylate (PMMA)) or conducting polymers (e.g.,
polyaniline (PANI) and polypyrrole (PPy)).
The preparation of magnetic polymer particles can be generally classified into three
categories as shown in Figure 1a particles with a magnetic core-polymer shell, Figure 1b
particles with a polymer core-magnetic shell, and Figure 1c magnetic particles embedded
in polymeric materials. One of the strategies to prepare these structures is to synthe-
size magnetic nanoparticles and polymer microspheres separately and then assemble the
two parts by exploiting the physical interaction between them. A second method is in
Polymers 2021, 13, 512 3 of 20

situ precipitation of iron oxide nanoparticles on the polymer’s surface in the presence
of polymeric microspheres. A third method is to polymerize monomers in the presence
of magnetic nanoparticles; the most effective method is heterogeneous polymerization
such as mini-emulsion polymerization [39], inverse emulsion/microemulsion polymeriza-
tion [40,41], conventional emulsion polymerization [42], and emulsifier-free mini-emulsion
polymerization [43]. These magnetic polymer composites are described in detail in the
following sections.

Figure 1. Various morphologies of magnetic polymer nanoparticles: (a) Magnetic core-polymer shell,
(b) polymer core-magnetic shell, and (c) magnetic particles embedded in a polymeric material.

2.1. Magnetic Iron-Based Polymer Composites

2.1.1. Iron Oxide
Among various magnetic particles, iron oxide nanoparticles have been extensively
used by the magnetic community. In particular, iron has the highest saturation magnetiza-
tion at room temperature, and its Curie temperature is sufficiently high. Consequently, iron
has received considerable attention in most practical applications. However, iron’s main
drawback is likely to be its reactivity, especially with moisture and oxygen. Fortunately,
the use of polymers as protective agents for zero-valent iron nanoparticles significantly
improves their usability. Various types of iron oxides such as magnetite (Fe3 O4 ), hematite,
and gamma iron oxide (γ-Fe2 O3 ) phases are available.
In recent years, hollow magnetic composite particles have been introduced. Because
of the low particle density resulting from the cavity inside the shell of hollow particles,
magnetic hollow particles can provide long-term stability, especially for MR fluid appli-
cations. Choi et al. [44] synthesized hollow polydivinylbenzene@Fe3 O4 (h-PDVB@Fe3 O4 )
nanoparticles with a relatively small density via a distillation-precipitation polymerization
technique; these nanoparticles are widely used in targeted drug delivery and nano-reactor
systems because of their unique structure. Uniform-sized polydivinylbenzene was first
coated on silica particles, and it was followed by a SiO2 etching process involving hydrogen
fluoride. Fe3 O4 nanoparticles were then synthesized on the hollow polydivinylbenzene
surface by a co-precipitation method by using FeCl3 ·6H2 O, FeSO4 ·7H2 O, sodium hydrox-
ide, and so on. The more uniform the particle size, the easier the particle aggregation for a
given magnetic field, which can improve the performance of the MR fluid. Figure 2a shows
a transmission electron microscopy image of h-PDVB@Fe3 O4 particles with a relatively
narrow particle size distribution of 670 ± 33 nm. The figure shows, to some extent, that
the particles can be used in MR fluids and will obtain a relatively good output. Note that
in the case of an inorganic coating on the magnetic particles, Agustin-Serrrano et al. [45]
reported that a silica-coated-magnetite-particle-based MR fluid showed interesting yield
stress behavior at a threshold magnetic field strength.
Iron oxide composites formed with polymers such as PS or PMMA also show enhanced
dispersion stability of the magnetic particles for MR applications. Kim et al. [46] fabricated
Fe3 O4 -encapsulated PS hybrid particles via a mini-emulsion polymerization process, while
Polymers 2021, 13, 512 4 of 20

Chae et al. [47] synthesized PS/Fe3 O4 particles consisting of a PS surface covered with
Fe3 O4 nanoparticles by the Pickering emulsion polymerization technique with better
dispersion stability. Note that Pickering emulsion polymerization does not require a
traditional organic surface active agent, which is difficult to eliminate or recycle after
polymerization, as the solid particle is used as a stabilizer. Therefore, this technique has
the advantages of low toxicity, few bubbling problems, simple technology, and green
environmental protection. Gao et al. [48] and Ahn et al. [49] also used Pickering emulsion
polymerization to form PMMA core-Fe3 O4 and Fe2 O3 shell structures, respectively.
The control of the particle size of the emulsion facilitates the maintenance of the stabil-
ity of the emulsion and allows new functions be provided to the emulsion. In this context,
the Shirasu porous glass (SPG) membrane emulsification technique, which can provide
useful water/oil/water (W/O/W) emulsion in high yield, is considered to be a mild and
low-energy-consumption technique for effectively controlling the size of microcapsules.
This technique improves the possibility of preparing various monodisperse polymer micro-
spheres. Gao et al. [50] synthesized novel core/shell shaped hybrid nanoparticles of Fe3 O4
embedded in PS with a narrow size distribution of 127 nm by an SPG membrane technique.
Uniform homogeneous styrene monomer was first injected from the inner surface of the
membrane into the outer aqueous dispersion phase by applying pressure with nitrogen.
The synthesized Fe3 O4 entered the styrene monomer with the help of sodium dodecyl
sulfate (used as a surfactant), and it was followed by the polymerization of PS.

Figure 2. Images of iron-based magnetic polymer composites: TEM images of (a) hollow
polydivinylbenzene@Fe3 O4 (Choi et al. [44], ©American Chemical Society, 2019), (b) polystyrene
(PS)/Fe3 O4 (Kim et al. [46], ©The Polymer Society of Korea and Springer, 2018), (d) polypyrrole-
coated Fe3 O4 hybrid particles (Choi et al. [51], ©The Royal Society of Chemistry, 2013), and (e)
PDPA/Fe3 O4 composite (Dong et al. [52], © Springer Nature, 2018). (c) Scanning electron microscopy
image of PS/Fe3 O4 particles (Choi et al. [47], ©WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim,
Germany, 2018).

Dual stimuli-response composite particles with both magnetic component and con-
ducting polymers have aroused the interest of a wide range of researchers, including
those in the fields of electrorheology and magnetorheology. Choi et al. [51] synthesized
PPy-coated Fe3 O4 magnetic composite particles without using an initiator and studied
their double excitation response under both electric and magnetic fields. During the poly-
merization of PPy, Fe3+ in the synthesized Fe3 O4 , which was immersed in deionized water
Polymers 2021, 13, 512 5 of 20

in advance, seeped from the surface into the polymerization reaction system, and therefore,
the polymerization process could be completed without using an initiator. Dong et al. [52]
synthesized organic-inorganic poly(diphenylamine) (PDPA)/Fe3 O4 particles via a sim-
ple fabrication technique and examined the ER and MR characteristics of both types of
particles, Kwon et al. [53] synthesized magnetic smart particles that were composites of
fibrous-structured PANI and Fe3 O4 , and Lee et al. [54] synthesized Fe3 O4 /poly(o-anisidine)
nanoparticles with a core-shell structure via oxidation polymerization. While the associa-
tion of conducting polymers provided extra ER functionality, it has been found that the
saturation magnetization and magnetic induction of magnetic polymer particles decreases
with an increase in the polymer concentration [55]. Therefore, it is necessary to care-
fully modulate the size and amount of magnetic nanoparticles in these polymer magnetic
composite particles to obtain the best magnetic properties [56].

2.1.2. Carbonyl Iron

Soft-magnetic carbonyl iron (CI) microbeads with a high purity (>98%) and unique
spherical morphology have been widely used in MR systems, and they have attracted both
academia and industry because of their potential for commercial use. Nonetheless, CI
particles usually have serious dispersion problems because of the significant difference in
density between the dispersion medium and the magnetic particles. Furthermore, in engi-
neering applications, bare CI particles may undergo an oxidation process with the passage
of time. Many core-shell-type CI-polymer microspheres have been studied to overcome this
drawback. In particular, ribbon-like PPy has been used for surface modification [57]. In this
process, CI particles were initially treated with aqueous cetyltrimethylammonium bromide
cationic surfactant solution and then the polymerization of PPy was initiated by adding
ammonium persulfate. Although the MR effect was reduced because the CI particles were
coated with polymers, the sedimentation of the liquid could remain stable for tens of
hours. In another study, CI particles were coated with cholesteryl groups via a two-step
reaction [58]. In this process, CI particles are first treated with (3-aminopropyl)triethoxy
silane (APTES) to form amino groups on their surface and cholesteryl chloroformate is then
added to CI particles coated with cholesteryl groups. This coating smoothes the surface of
the magnetic material and considerably improves the thermal stability of CI under oxygen
atmosphere, and the settling stability and re-dispersibility of its suspension in silicone
oil. Cvek et al. [59] investigated the chemical stability and cytotoxicity of poly(glycidyl
methacrylate) (PGMA)-grafted CI particles. These CI-PGMA particles, which are used
in medical applications such as magnetic drug targeting systems, were found to have no
cytotoxicity from an in-vitro cytotoxicity test conducted according to ISO standards. In
another study, CI particles’ surface was grafted with a simple covalent coating with short
poly(n-butyl acrylate) (PBA) chains via an atom-transfer radical polymerization (ATRP)
technique [60]. First, the bare CI particles’ surface was modified with APTES and then
n-butyl acrylate was surface-initiated on the particles. The CI-PBA particles provided
a yield stress, reaching values sufficient for use in industrial applications, and showed
improved chemical and sedimentation stability.
Cho et al. [61] performed in situ dispersion polymerization to prepare composite
particles with a CI core and a PMMA shell. The CI particle surface was grafted with organic
molecules (e.g., acrylic acid or methacrylic acid) before the polymerization, as shown in
Figure 3. Various conducting polymers have been used for coating CI particles, such as
polyindole [62], PDPA [63], PANI [64], and polydopamine [65], through chemical oxidation
polymerization to reduce the density of CI particles. These magneto-conductive polymer
systems were developed not only to improve the dispersion stability of MR fluids, but
also to provide great possibilities in the fields of application of both MR fluid and ER
fluid systems [66].
Polymers 2021, 13, 512 6 of 20

Figure 3. Schematic of the preparation process for polymer-coated carbonyl iron (CI) particles
(Cho et al. [61], © IEEE, 2004).

2.2. Other Magnetic Meltallic Polymer Composites

Next to iron-based materials, cobalt-based magnetic nanoparticles are known to be
the most widely used, with high magnetic susceptibility and high saturation magneti-
zation values. However, their disadvantage is their instability, which results from their
strong magnetism and van der Waals force. They tend to form agglomerates easily, and
therefore, their practical application is often limited. Coating these particles with poly-
mers is a practical and effective method for inhibiting their oxidation and agglomeration,
and it improves the long-term colloidal stability of their magnetic dispersions in solution.
Korth et al. [67] synthesized PS-coated cobalt nanoparticles in which the polymeric shell
formed a glossy coating that encapsulated the 1D structure of the assembled nanoparticle
chains. Chatterjee et al. [68] prepared copper-nickel alloy nanoparticles through chemical
reduction and encapsulated them in polyethylene glycol nanoparticles by using an emul-
sion and a chemical cross-linking method. Spinel ferrites (M× Fe3−× O4 ), such as MgFe2 O4 ,
MnFe2 O4 , CoFe2 O4 , NiFe2 O4 , and ZnFe2 O4 have also been combined with polymers as
shown in Figure 4. Kim et al. [69] prepared raspberry-like core-shell composite particles,
which comprised a PANI core and a zinc ferrite shell, through polymerization by the
Pickering emulsion technique. Table 1 presents a list of magnetic polymer composites.

Figure 4. TEM images of magnetic polymer composites: (a,b) Co-PS nanoparticle chains (Korth et al. [67], ©American
Chemical Society, 2006) and (c) Cu–Ni/polyethylene glycol magnetic polymer (Chatterjee et al. [68], Elsevier B.V., 2005).

3. MR Characteristics
3.1. MR Fluids
When soft magnetic particles are suspended in nonmagnetic liquids (e.g., paraffins,
natural fatty acids, minerals, hydrocarbons, and silicon-based liquids), these free-moving
particles are polarized by an applied H and made to connect to neighboring particles
aligned in the direction of the applied H, as shown in Figure 5 [18]. A well-known mecha-
nism to explain MR behavior is the magnetic dipole interaction between particles because
Polymers 2021, 13, 512 7 of 20

of particle magnetization. In the linear magnetization region, the magnetic moment m of a

magnetic particle with radius a is field-induced and can be expressed as [51],

m = 4πµ0 µcr βa3 H (1)

where µ0 is the vacuum permeability (4π × 10−7 ), µcr is the relative permeability of the
medium, and β is the contrast factor expressed as:

µ pr − µcr
β= (2)
µ pr − 2/µcr

here, µpr is the permeability of the particles. In this low-magnetization region, the magnetic
interaction between two magnetic particles is proportional to H2 . In a high-magnetic-field
region, the magnetic moment is independent of the magnetic field strength as shown in
Equation (3), where Ms is the saturation magnetization of the magnetic particle. This
implies that the interaction between the particles is no longer affected by an increase in the
external field.
m = 4πµ0 µcr βa3 Ms (3)

Table 1. Preparation methods for various magnetic polymer composites and their magnetic properties (the abbreviation
“N.D.” denotes “not determined”).

Density M s Value
Magnetic Particles Polymer Method Ref.
[g/cm3 ] [emu/g]
Fe3 O4 Polydivinylbenzene Distillation-precipitation polymerization 1.83 41 [44]
Fe3 O4 Poly(diphenylamine) Coprecipitation 2.44 77.1 [52]
Fe3 O4 Poly(o-anisidine) Chemical oxidation polymerization 2.52 36 [54]
Fe3 O4 Polystyrene Mini-emulsion polymerization 2.8 27 [46]
Fe3 O4 Polystyrene Pickering emulsion polymerization 1.69 59 [47]
Fe3 O4 Polystyrene Shirasu porous glass membrane technique 2.29 31.7 [48]
Fe2 O3 Poly(methyl methacrylate) Pickering emulsion polymerization 1.68 20.05 [50]
Fe3 O4 Polyaniline Micelle-assisted self-assembly method N.D. 39.4 [53]
CI Polypyrrole In situ polymerization N.D. ≈120 [57]
CI Cholesteryl groups Surface modification N.D. ≈180 [58]
CI Poly(glycidyl methacrylate) Atom transfer radical polymerization N.D. 215 [59]
CI Poly(n-butyl acrylate) Atom transfer radical polymerization N.D. 227 [60]
CI Polyindole Chemical oxidation polymerization 7.3 180 [62]
CI Poly(diphenylamine) Oxidative dispersion polymerization 7.42 191 [63]
CI Polyaniline Chemical oxidation polymerization 4.21 136 [64]
CI Polydopamine In situ self-oxidative polymerization 6.17 135 [65]
CI Poly(methyl methacrylate) In situ dispersion polymerization 4.5 151 [61]
Metallic cobalt Polystyrene Nitroxide-mediated polymerization N.D. 38 [67]
Copper nickel alloy Polyethylene glycol Oil/water emulsion N.D. 45 [68]
ZnFe2 O4 Polyaniline Pickering emulsion polymerization 5.4 73.7 [69]

On the other hand, three different modes of operations have been used to describe
MR suspensions: Valve (pressure) mode, shear mode, and squeeze mode. The valve mode
includes stationary poles and fluids perpendicular to the direction of the magnetic field.
The poles of the shear mode move parallel to the flow, and the force is in line with the
direction of the magnetic field and the direction of the aggregate particle chain in the
squeeze mode [70,71]. The shear mode is the most common rheological test mode used to
measure the rheological properties of MR suspensions. At low shear rates, the mesoscopic
structure is robust and can withstand shear-induced stress. However, hydrodynamic
stress overcomes the interaction between particles and breaks the shear-induced chain
mesoscopic structure, thus, starting to flow at a higher shear rate. MR suspensions exhibit
a residual stress (yield stress) that increase with the magnetic field strength at that time.
The rheological characteristics of MR fluids can be analyzed using a simple steady
shear and a dynamic mode. The flow curve of MR fluids can be obtained by performing
the steady shear test, which involves two controlled shear rates and controlled shear stress
methods. At a low shear rate, the mesostructure is robust and can withstand shear stress.
However, as the shear rate increases, the shear stress overcomes the interaction between
Polymers 2021, 13, 512 8 of 20

the magnetic particles and
breaks the chain structure, and the fluid then starts to flow,
defining the yield stress τy . While the static yield stress is considered to be the minimum
shear stress causing the fluid to flow, the dynamic yield stress (τdy ), which is the stress
corresponding to the continuous failure of the aggregate, can be extrapolated using a flow
curve to the zero shear rate [72]. Some rheological models for MR fluids are listed in Table 2,
where t1 and t2 are time constants and η∞ is the viscosity at high shear rates. All of the
models can predict τdy only by extrapolating the flow curve. The Bingham fluid model is
the simplest model to fit the flow curve, and the Herschel–Bulkley model is also commonly
used because of its simple form compared with other models. All models, except the
Seo-Seo model, predict only the dynamic yield stress, which is obtained by extrapolating
the shear stress curve back to zero shear rate and which is strongly influenced by the
shear rate range and the selected rheological model [73,74]. However, with an increase
in the shear rate, the flow is hindered more at high magnetic fields [75,76], as shown in
Figure 6a. The flow shows a minimum value in the flow curve, and Kim et al. [74] used
both Bingham and Cho–Choi–Jhon models to fit the flow curves of Fe2 O3 and Fe2 O3 -PS
magnetic polymer.

Figure 5. Schematic of the microstructure in a magnetorheological (MR) fluid before and after the
application of an external magnetic field (Liu et al. [66], ©The Polymer Society of Korea and Springer
Nature B.V., 2013.

Table 2. Representative rheological models for viscoplastic yielding fluids.

Rheological Model Equation Ref.

.
Bingham τ = τy + η γ, |τ | > τy [77]
.n
Herschel–Bulkley τ = τy + η γ , |τq| > τy [77]
√ √ .
Casson τ = τy + η γ [77]
.

.
Papanastasiou τ = τy 1 − exp  −nγ + η γ  [32]
Cho–Choi–Jhon τy 1 . [78]
τ= . a + η∞ 1 + . β γ
1+ ( t1 γ ) ( t1 γ )
Polymers 2021, 13, 512 9 of 20

Figure 6. (a) Plots of shear stress vs. shear rate for pure Fe2 O3 (closed) and PS/Fe2 O3 (open) MR fluids at various magnetic
field strengths (Kim et al. [74], ©American Chemical Society, 2013) with Bingham (dotted line) and Cho–Choi–Jhon (solid
line) fits. (b) Magnetization curves of CI and CI/polydopamine powder as a function of the magnetic field strength
(Kim et al. [65], ©Springer-Verlag Berlin Heidelberg, 2015).

Although there are many factors affecting the yield stress of MR fluids, the external
magnetic field is the most dominant factor. The relationship between τy and H is expressed
by a power law ( τy ∼ H n ) [78,79]. For linear magnetic polymer particles with low perme-
ability, n usually shows quadratic dependence (n = 2) at low magnetic fields. However, for
intermediate or high field strengths, n is expected to be 1.5, as shown in Figure 6b [65]. A
new universal yield stress correlation can be described as,
 √ 
tanh H0 /Hc
τy = αH02 √ (4)
H0 /Hc

where α is relevant to the susceptibility of the MR fluid and Hc is the critical magnetic field
strength. The parameter τy has two types of limiting behavior in relation to H:

τy = αH02 for H0  Hc , (5a)

√
τy = α Hc H03/2 for H0  Hc (5b)
Due to the difficulty in separating the two different regions when using Equation (4),
Seo [79] proposed a rather simpler equation that could fit the experimental data well with
one parameter:
3  p 
τy ( H0 ) = αH02 1 − exp −m0 H0 (6)

Normalizing Equation (4) with Hc and setting τy,0 = αHc 3/2 yields the following
dimensionless equation:   p 
τ̂ = Ĥ 3/2 1 − exp −m0 Ĥ (7)
√
where Ĥ = HHc and m = m0 Hc .
Viscoelastic properties, including the storage ( G 0 ) and loss (G 00 ) modulus obtained
from dynamic oscillation tests, also strongly influence the application of MR fluids. In
Figure 7a, Gao et al. [50] examined G 0 and G 00 as a function of strain (γ) for strain values
from 0.001% to 200% at a constant frequency of 6.28 rad/s under different magnetic field
strengths. In the low-strain region (linear viscoelastic range γLVE ), G 0 and G 00 showed a
constant value, indicating that the MR fluid behaved like an elastic solid with a certain
Polymers 2021, 13, 512 10 of 20

hardness. When the strain (γ) exceeded the critical value of γLVE , the G 0 and G 00 curves
dropped rapidly because of the deformation of the chain structure. Figure 7b shows the
elastic stress, which can be defined as Equation (8). This elastic stress explains the change in
the properties of the MR fluid from solid-like to liquid-like properties throughout the entire
strain range, and when the solid-like structure begins to break, the yield point becomes
apparent in one step by which the elastic yield can be obtained just like dynamic yield
stress, which was discussed earlier:
τ 0 = G0 γ (8)

Figure 7. Strain amplitude sweep for an Fe3 O4 -PS-composite-based MR fluid (10 vol %, 100 cSt silicone oil) as a function of
(a) storage modulus vs. strain and loss modulus vs. strain (closed symbols: G 0 ; open symbols: G00 ) and (b) elastic stress vs.
strain (Gao et al. [48], ©Springer Nature, 2017). (c) Storage modulus of pure Fe3 O4 (open) and PANI@Fe3 O4 (closed) as
a function of the angular frequency (Kwon et al. [53], ©IEEE, 2016). (d) Relaxation modulus of CI/PANI calculated from
G 0 (ω ) and G00 (ω) obtained from a frequency sweep test (Min et al. [64], ©Elsevier B.V., 2017).

The angular frequency sweep test is also usually used to describe the MR properties
of MR fluids. As shown in Figure 7c [53], in a previous study, the storage of Fe3 O4 and
PANI@Fe3 O4 magnetic polymer composites was expressed as a function of the angular
frequency (1–100 rad/s) for a constant γ of 0.05%. G 0 was considerably higher than G00 ,
indicating that under the applied H, at γLVE , the MR fluid predominantly showed solid-like
properties. Figure 7d [64] shows the relaxation modulus G (t) of the CI/PANI composite as
a function of time; G(t) can be determined from G 0 (ω ) and G00 (ω) by using the Schwarzl
equation [80], which is given by Equation (9) below. While the raw data of G0 and G00
is a function of ω note that ω is related to 1/t. The Schwarzl equation has been widely
Polymers 2021, 13, 512 11 of 20

used not only for MR materials but also for other material systems, including polymer
nanocomposites [81]:
ω 
G (t) = G 0 (ω ) − 0.566G 00 + 0.203G00 (ω ) (9)

2 ω =1/t

The relaxation moduli of the MR fluid saturated over time, showing distinct solid-like
behavior under the applied H such that the strong magnetic-field-induced force between
the magnetic particles did not relax with time, unlike the case without H.

3.2. MR Elastomers
MR elastomers are similar to MR fluids in terms of their physical mechanism, and
they comprise magnetic particles, an elastomer matrix, and an additive. The additive plays
a crucial role in the MR elastomer system in minimizing the aggregation and sedimentation
of filler particles and provides lubricating properties [82]. However, compared with the
fabrication method of MR fluids, there are some differences in the fabrication method used
for MR elastomers as shown in Figure 8. The preparation process of MR elastomers includes
mixing, curing and magnetic particle orientation. The magnetic particle chain formation is
initiated in the pre-yield region, while it is activated in a post-yield continuous shear or flow
regime [83]. Differently magnetized particles such as Ni [84], CoFe2 O4 [85], and FeCo3 [86]
have been studied in MR elastomers. Apart from the magnetic particles in MR elastomer
systems, the MR effect of magnetic particles coated with a polymer in MR elastomers
is crucial. MR elastomers have several drawbacks such as poor particle dispersibility,
wettability problem, low chemical stability, and short durability [87]. These disadvantages
can be eliminated by grafting CI particles with poly(trimethylsilyoxyethyl methacrylate)
(PTEMATMS) via ATRP. Such grafting clearly enhances magnetostriction, the damping
factor, the sensing capability, and even mechanical properties. From a MR perspective
of CI-g-PTEMATMS, the G 0 of MR elastomers increases when CI fillers are added since
rigid inorganic particles have higher stiffness property than polymer matrices [88,89]. The
introduction of CI-g-PTEMATMS particles in MR elastomeric systems enhances G00 , which
can be related to the energy dissipating heat caused by friction between the matrix and
particles. Furthermore, according to Fuchs et al. [90], the ATRP process has been adopted for
the surface polymerization of CI particles with fluorinated styrene. The application of this
process has led to remarkable durability increase. The effect of the process can be gauged
from the fact that an MR elastomer with its surface coated with iron particles requires an
increase of only 3% to achieve 20% strain. Whereas, an MR elastomer has to increase 17%
in order to achieve the limit. MR elastomers with an iron particle coating show significant
durability potential, as inferred from the force-displacement result, which can be used as a
vibration isolator. In contrast to the low stiffness shown by classic elastomer composites,
which is generally associated with the cross-linking of long chains, MR elastomers show
higher elastic modulus, up to 30%, under the application of a magnetic field [91].
According to Figure 9 [86], CI particles show a smooth and clean surface, whereas CI-
g-poly(trimethylsilyloxyethyl methacrylate (PHEMATMS) particles have a rough surface
because of the 15 nm PHEMATMS-grafted layer.
Polymers 2021, 13, 512 12 of 20

Figure 8. Schematic of the fabrication process for isotropic and anisotropic MR elastomers
(Kwon et al. [84], ©MDPI, 2018).

Figure 9. TEM images of (a) bare CI and (b) a single particle of CI-g-poly(trimethylsilyloxy)ethyl
methacrylate (Mordina et al. [86], ©American Chemical Society, 2014).

4. Applications of Magnetic Polymer Composite Particles

4.1. MR Applications
Over the past several decades, MR fluids have attracted considerable interest, and
their promising properties have led to their use in many industrial applications. Parlak
et al. [92] used time-dependent computational fluid dynamics analysis to simulate the
motion of a piston head in an MR damper with a transient deformation mesh. A quasi-
static model was proposed to calculate the damping force in the annular clearance and
the specified thickness of the plug core. Yang et al. [93] developed a tiny tactile button
driven by MR fluid that delivered kinesthetic information, or real button sensations, to
users of small electronic devices. This button consists of a yokesleet housing containing a
solenoid, plunger, elastic spring, and MR fluids. The solenoid coil is attached to the bottom
of the housing surrounding the yoke, and the plunger and elastic spring are placed inside
the solenoid coil. When an electric current is applied to the solenoid coil, the flux fluid
is activated in the gap between the yoke and the plunger, and it forms a granular chain.
The MR fluid chains produce shear stresses that are transmitted to the user in the form of
resistance on the contact plate.
Chen et al. [94] developed an MR actuator for use as an intelligent actuator for auxiliary
knee stents. It could be used to provide controllable torque in the auxiliary knee stent. It
comprised a DC motor, an external cylinder connected to the upper leg, an MR fluid for
the shearing mode to generate or transmit torque, and an internal cylinder connected to
the shaft. Lee et al. [95] developed a prototype tactile display containing MR fluid. This
tactile display device simulated the skin of the fingers to sense sensations of contact, such
as compliance, friction, and surface topography. Patil et al. [96] introduced a finite element
Polymers 2021, 13, 512 13 of 20

analysis model and an analysis method for analyzing an MR brake in detail as presented
in Figure 10a. In another study, a model was developed to describe centrifugation, and an
MR clutch design was developed to alleviate the sealing problem [97].
Choi et al. [98] proposed a semiactive controlled MR suspension for vibration control
of passenger car engines. The upper part of the mount comprised the main rubber to
provide appropriate stiffness and damping properties. The MR fluid moved through the
gap between the shell and the magnetic pole and was controlled by the magnetic field
strength. Lee et al. [99] used a biopolymer of xanthan gum (XG) to coat the surface of
CI particles to improve the MR polishing performance. In existing commercial systems,
the aqueous MR fluids used in QED technology polishing systems comprise CI particles,
nonmagnetic abrasives, deionized water, and stabilizers. When the nonmagnetic MR fluid
is moved to the gap on the wheel, the appropriate part of the gap is magnetized by an
electromagnet. The magnetized MR fluid removes material and is then transported outside
the magnetic field, where it is removed from the wheel. In another study a novel tactile
device using MR fluid was presented. It could provide rejection information about an organ
to a surgeon [100]. When the diaphragm was compressed by the operator, the operator
could feel the touch of the MR fluid, and the sense of touch could be controlled through
magnetic fields.
General applications of MR elastomers include adaptively tuned vibration absorbers
(TVAs), vibration isolators, dampers, vehicle shock absorbers, sandwich beams, actuators,
and sensors. The intelligent behavior of MR elastomers, which work in the shear mode,
has been practically applied in automobile suspensions. Ginder et al. [101] developed a
suspension bushing, which is a pioneer application of MR elastomers. The TVA developed
by them is a single-degree-of-freedom system that can increase the natural frequency from
500 Hz to 610 Hz in the range of the maximum available magnetic field. MR elastomers are
also used to develop active or semiactive isolators that can work in both horizontal and
vertical directions. For example, Yang et al. [102] developed an isolator that works in the
shear mode with an MR elastomer, Mikhailov et al. [103] developed an active damper that
could be used for micro- or nano-positioning drives of microisolator objects as shown in
Figure 10b, and Sun et al. [104] developed MR elastomer isolators to protect multistore
buildings from the impact of seismic events.
Adaptive sandwich structures are another application for which MR elastomers are
potential candidate materials. Dyniewicz et al. [105] studied the behavior of sandwich
beams by placing MR cores at the ends of beams, and Szmidt et al. [106] proposed a new
type of MR-elastomer-based sandwich beam in which the MR elastomer is clamped at the
edge with two separate cantilevered beams. MR elastomers are also potential candidate ma-
terials for sensor components. Ge et al. [107] developed a displacement sensor by coating a
porous MR elastomer with carbon nanotubes. A tactile sensor is another type of sensing de-
vice in the field of MR elastomers, Kawasetsu et al. [108] developed a flexible tactile sensor
based on an MR elastomer that could detect normal forces and vertical deformation in an
application as given in Figure 10c, and Lee et al. [109] developed a micro-cantilever beam
with MR elastomer characteristics. More recently, Xu et al. [110] used an MR elastomer as a
polishing composite material to perform magnetically controlled polishing.
MR elastomers are also used in biomedical applications, for purposes such as drug
and cell delivery for active burns. Fahrni et al. [111] created high-aspect-ratio lying artificial
cilia with a length of 300 µm based on lithographic techniques. In another study, a new
type of an active porous scaffold controlled by a magnetic field was used to transfer
different biological agents by alginate brine gel and magnetite particles [112]. In yet another
study, the engineering adjustable active surface morphology of micron-scale columns
was developed by using magnetic polymer particles controlled by an electromagnetic
field to prevent serious infections from being caused by the formation of biofilms on
medical devices [113].
Polymers 2021, 13, 512 14 of 20

Figure 10. Applications of (a) a finite element analysis model of a proposed MR brake (Patil et al. [96], ©Elsevier Ltd., 2016),
(b) a sectional view of an active damper based on an MR elastomer (Mikhailov et al. [103], ©Elsevier B.V., 2016), and (c) the
basic structure of a flexible tactile sensor (Kawasetsu et al. [108], ©MDPI, 2018).

4.2. Other Applications

Owing to their physical and mechanical properties, polymer-encapsulated magnetic
filler particles with a diameter of less than 1 µm have been widely used in pharmaceutical,
cosmetic, paint, and other industries. Magnetic separation of labeled cells and other
biological entities, therapeutic drugs, gene and radionuclide delivery, radiofrequency
methods of tumor catabolism through hyperthermia, and contrast enhancers for magnetic
resonance imaging applications are the most important applications of magnetic polymer
composite particles [114].
There are several ways to minimize environmental contaminants using magnetic
nanoparticles. Iron is one of the strong agents that degrades a wide range of organic and
inorganic materials in contaminated chlorinated solvents and water sources. Moreover,
surface sorption and co-precipitation facilitate the removal of contaminants in air or wa-
ter environments through the generation of iron oxide/hydroxide [56,115–117]. Hybrid
magnetic nanoparticles have been developed using PMMA and super-paramagnetic iron
oxide nanoparticles for the removal of heavy metals such as Cu, Co, Hg, and Pb under
a magnetic field [118]. The possible contaminant removal mechanisms when magnetic
nanoparticles are used include co-precipitation, electrostatic attraction, and high reductive
reactivity between molecules [100]. Furthermore, magnetic nanoparticles can be used
as nonabsorbents for water purification, and they can increase the removal efficiency of
contaminants by acting as immobilization carriers [118].
Ligand exchange methods have been developed for prefabricated magnetic nanoparti-
cles, to overcome the limitation of functional surfactants. Extensive studies on the function-
alization of gold and semiconductor nanoparticles through ligand exchange strategies have
been reported, demonstrating the feasibility of this approach at the nanoscale. Ligating
groups such as thiols, COOH, diols, and phenols have been used to coordinate magnetic
nanoparticles. Fauconnier et al. [119] investigated the 2,3-dimercaptosuccinic acid onto
electrostatically stabilized maghemite colloids to conjugate the proteins onto thiolated mag-
netic nanoparticles. Rahj et al. [120] systematically studied the modification of bidentate
enediol compounds containing Fe nanoparticles by using a series of compounds and evalu-
ated them by X-ray absorption spectroscopy. On the basis of this research, Xu et al. [121]
developed a bifunctional small molecule dopamine surfactant to functionalize magnetic
nanoparticles through ligand exchange. In addition, dendritic coating functionalization
of magnetic nanoparticles was also achieved. Through ligand exchange reaction with
polyamide dendrites, Kim et al. [122] prepared robust and dimensionally stable coatings.
The functionalization of magnetic nanoparticle terminal polymer corona was studied
using surface initiated polymerization, which can precisely change the molar mass and
composition of the polymer chains growing on a colloidal surface. Wang et al. [123] used a
combination of ligand exchange and surface-initiated ATRP to prepare core-shell PS-grafted
γ-Fe2 O3 nanoparticles. Marutani et al. [124] and Ninjbadgar et al. [125] demonstrated that
PMMA-coated core-shell colloids could be prepared by covalently anchoring the ATRP-
starting sites to magnetite nanoparticles using silane coupling agents. Gelbrich et al. [126]
prepared thermo-responsive magnetic core-shell nanoparticles by using surface-initiated
Polymers 2021, 13, 512 15 of 20

ATRP of 2-methoxy methyl methacrylate from a Fe3 O4 colloidal initiator. Surface-initiated

nitroxide-mediated polymerization has also been investigated for the preparation of
polymer-coated core-shell nanoparticles. Matsuno et al. [127] synthesized a phospho-
ric acid functional Hawker-type alkoxyamine based on TEMPO to bind the initiator portion
tightly to the iron oxide surface.

5. Conclusions
Functionalized magnetic polymer nanoparticles have high potential for development.
These magnetic polymer nanoparticles have broad application prospects in the fields of non-
magnetic drug delivery, biomarker and biological modification, etc. [128–131]. However, a
thin polymer coating cannot protect reactive magnetic particles against oxidation. Another
disadvantage of polymer-coated nanomagnetic particles is that the thermal stability of
their coating at elevated temperatures is relatively low. Therefore, in the final application,
ensuring the careful regulation of the thickness of the polymer coating may be a solution
for the synthesis of magnetic polymer composites by using appropriate methods.
In this review, magnetic polymer composite particles are introduced by their com-
position (including two parts: Magnetic particles of iron-based materials such as Fe2 O3 ,
Fe3 O4 , and CI and other magnetic particles such as cobalt and spinel ferrites, and polymers
such as PS, PMMA, PEG, and PANI) and synthetic methods. Fe3 O4 is the most attractive
magnetic particle owing to its high saturation magnetization, soft magnetic behavior, easy
synthesis, suitable particle shape and size, and low density. The most important role of a
polymer coating on the surface of magnetic particles is that a less dense polymer shell can
significantly improve the sedimentation stability of MRF. Furthermore, coating magnetic
particles with a conductive polymer enables the composite to conduct electricity, and this
material can be used in systems that provide a dual stimulus response in both electric and
magnetic fields [132].
Magnetic polymer materials have also been widely used in MR fluid and MR elastomer
systems. The flow curve of MR elastomers can be fitted with a variety of rheological models
to find the yield stress, which is an important parameter of MR fluids. The relationship
between τν and H is expressed by a power law (τν ~Hn ) in which n changes with the mag-
netic field strength from 2 to 1.5 [133]. Viscoelastic properties can be determined through
dynamic oscillation tests. Of all the magnetic particles, CI-based magnetic polymers show
relatively excellent MR effect, but the sedimentation stability of these composites is still
a problem that should be resolved. Furthermore, polymer-coated iron particles used in
MR elastomers also show significant durability potential in the force-displacement result.
Finally, we have provided a brief overview of the applications and prospects of magnetic
polymer composites. It is hoped that these applications will lead to fruitful results and help
expand their commercial application.

Author Contributions: Q.L. and K.C. prepared the draft together with the guidance of H.J.C. and
J.-D.N. H.J.C. initiated and finalized this review paper. Q.L. and K.C. contributed equally to this
work. All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by National Research Foundation of Korea (2018R1A4A1025169).
Conflicts of Interest: The authors declare that they have no conflict of interest.

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