Physica B 448 (2014) 7376

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Physica B
journal homepage: www.elsevier.com/locate/physb

Synthesis of dimorphic MR uid containing NiCo nanoowers

by the polymer assisted polyol method and study of its
magnetorheological properties
Injamamul Arief, P.K. Mukhopadhyay n
LCMP, Department of Condensed Matter Physics and Material Sciences, S.N. Bose National Centre for Basic Sciences, Salt Lake, Kolkata 700098, WB, India

art ic l e i nf o

a b s t r a c t

Available online 6 May 2014

Flower-like nanostructures of NiCo (1:1) in the presence of Jeffamine was synthesized by homogeneous
nucleation in 1, 2-propanediol for 3 h. Morphological characterizations performed by scanning and
transmission electron microscopy (FESEM and TEM) revealed the average size distribution of 700 nm
containing 2D nanosheets of
30 nm thickness. The nanoowers crystallize exclusively in face-centered
cubic structures and were conrmed by x-ray diffraction studies. Various factors, including nature of
polyol, concentrations of base and metal salts in precursor proved to affect the geometry of nanoowers.
Magnetic studies revealed the ferromagnetic nature of NiCo nanoowers with high saturation
magnetization and low coercivity (108.6 emu/g and 78.4 Oe). The enhanced shear properties and yield
stress of dimorphic MR uid containing nanoowers of NiCo in ferrouids can be attributed to stronger
microstructure formation in the presence of magnetic eld.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
NiCo alloy nanoower
Dimorphic MR uid
Amphiphilic polymer
Magnetosheological measurements

1. Introduction
The NiCo binary alloy is an important member of transition
metal alloys due to its diverse potential applications in microwave
absorption, magnetic resonance imaging contrast agents, magnetic
recording devices, magneto-optics, ferrouids and magnetorheological suspensions. Compared to conventional nanoscale materials,
NiCo nanostructures with hierarchical morphologies have often
been regarded as an important class of functional materials due to
their enhanced surface properties and varied range of architectures.
Hierarchic structures originate from the self-organization of nanoscale building blocks through various chemical or physical interactions. Magnetic properties of these nanostructures are often
superior to their single-domain counterparts. Hierarchical structures with cavities and/or pores endow higher surface area and
efcient diffusion of ultra-small nanoparticles of other materials. So,
these properties can be utilized in various application including
fabrication of hybrid magnetorheological (MR) uids, in energy
storage [1], catalysis [2] etc. Conventional MR uid contains micron
sized, soft magnetizable particles which are prone to settling [3].
Combining ferrouids (containing magnetic nanoparticles in
aqueous or organic carrier liquid) with micron sized particles in
MR uids can sufciently reduce settling tendency and increase

strength of chain-structure formed under applied magnetic eld

[4,5]. Depending on the shape morphologies and size of magnetic
particles, the strengths of MR uids can be tuned accordingly.
Therefore, continuous effort has been made to regulate shapes and
sizes of NiCo nanostructures. For the synthesis of NiCo hierarchic
nanostructures, polyol process proved to be one of the most
versatile, simple and cost-effective reduction method [6]. However,
hierarchical ower-like NiCo nanostructures using polyol as reducing agent-cum-solvent has not been successfully attempted before.
Here we report an amphiphilic polymer-assisted homogeneous
polyol reduction method to synthesize nanoowers composed of 2D
nanosheet-like subunits. Amphiphilic polymers represent a new class
of block copolymers and contain both hydrophilic and hydrophobic
parts to ensure versatile dispersibility and biocompatibility as they can
offer either hydrophilic or hydrophobic sites for capping [7]. Enhanced
magnetic properties of nanoowers, compared to other nanostructures proved to be useful for their use in MR uids. Moreover, a novel
MR uid consisting of ferrouids as carrier liquid and nanoowers as
dispersed phase was designed. Steady state magnetorheological
measurements were performed to rationalize the superior MR behavior of the MRF, in comparison to conventional MR uid.

2. Experimental method
n

Corresponding author. Tel.: 91 3323355706; fax: 91 3323353477.

E-mail address: pkm@bose.res.in (P.K. Mukhopadhyay).

http://dx.doi.org/10.1016/j.physb.2014.04.068
0921-4526/& 2014 Elsevier B.V. All rights reserved.

The synthesis of NiCo nanoowers was carried out by a typical

one-pot polyol reduction in presence of amphiphilic triblock

74

I. Arief, P.K. Mukhopadhyay / Physica B 448 (2014) 7376

copolymer
O,O0 -bis(2-aminopropyl)polypropyleneglycol-blockpolyethyleneglycol-block-polypropyleneglycol (Jeffamines ED-600
with approx. mol. wt. Mr
600, Sigma-Aldrich). In this process,
precursor solution was prepared by dissolving Ni (II) acetate
tetrahydrate (Z 98%, Sigma-Aldrich) and cobalt (II) acetate tetrahydrate (Z98.0%, Sigma-Aldrich) in 1, 2-propanediol (PrG, Loba
Chemie) with 1:1 M ratio. A PrG solution of Jeffamine (5 mL,
0.25 g) was added to precursor under owing argon gas for
30 min. Afterwards, aqueous potassium hydroxide (10 mL, 0.75 M)

hcp

(111)

Intensity (a.u.)

fcc

(100)

3. Results and discussions

(220)

(200)

40

added drop-wise to the precursor under constant stirring. The

resulting solution turned bluish-green due to the formation of
mixed metallic double hydroxide. The suspension was then quickly
transferred to a two-necked round bottom ask and heated to boil.
To boil off water, temperature of the suspension was maintained
at 130 1C for 20 min. Afterwards, reaction mixture was reuxed for
3 h. The resulting solution achieved homogeneity at the boiling
point of liquid polyol. Following the nucleation and growth phase,
black precipitate was formed at the bottom of vessel, indicating
formation of NiCo alloy. The puried NiCo suspension was
obtained by centrifugation and subsequent washing with Millipores water, acetone and absolute ethanol. In order to obtain NiCo
powder, suspension was dried in air at 60 1C.
For magnetorheological measurements, two 5 vol% MR uid
samples (MR1 and MR2) were prepared by dispersing exact
amount of NiCo nanoowers (density 7.6 g/cc compared to bulk
density 8.90 g/cc) in silicone oil (viscosity 30 mPa s at 25 1C) and
aqueous Fe3O4-based ferrouid, respectively (Cat. no. MSGW07,
viscosity o10 mPa s with average particle diameter
10 nm and
was a gift from Ferrotecs Corp., Japan).

50

60

70

80

2 (degree)
Fig. 1. x-Ray diffraction pattern of as-synthesized NiCoJeffamine ower-like
nanostructures composed of 2D-nanosheets. Peak for hcp-Co is also marked.

The crystallite structure of the resulting nanostructure was

determined by powder x-ray diffraction using PANalytical X'Pert
PRO diffractometer (scan range 2 40851) with monochromatic
Cu-K radiation ( 0.51418 nm) and is shown in Fig. 1. The
featured peaks at 2 44.61, 51.61 and 77.71 represent a facecentered cubic structure for NiCo nanostructure with presence of
hcp phase corresponds to (1 0 0) peak in the alloy. All the peaks
were identied and indexed to fcc NiCo alloy. Some unreacted

Fig. 2. FESEM images of JeffamineNiCo nanoower intermediates during reuxing after different reaction times: (a) 30 min, (b) 90 min, and (c) 180 min. (At bottom)
TEM micrograph and SAED of Ni51Co49 hierarchic nanostructures. Particle size distribution shown at bottom right.

I. Arief, P.K. Mukhopadhyay / Physica B 448 (2014) 7376

broad peak in the ZFC around 200 K. This is expected because the
magnetic nanostructures are by themselves ferromagnetic, but are
so dispersed that their overall magnetization is weak. The monotonic rise in FC curve also indicates to this effect.

4. Magnetorheological characterization
Magnetorheological studies were performed for MR uids
using Anton Paar Physica MCR 301 Rheometers with a parallel
plate geometry (plate gap 1 mm) at 25 1C. Steady state MR
rheograms (shear stress vs. shear rate) were shown in Fig. 4. The
rheological behavior shows that the ferrouid based system has a
higher yield stress between the two.
Since the behavior is evidently non linear, we tried to t
HerschelBulkley uid model [8] to describe it. The equation is
0 k_ n where is the shear stress, _ the shear rate, 0 the
yield stress (i.e. at zero shear velocity), and k and n are regarded as
model factors. Table 1 gives the tting parameters.
The examination of the table shows that while the zero eld
data do not t well with the model, the behavior under magnetic
eld is more reasonable. We see that there is a trend of enhancing
the yield stresses (0) and consistencies (k), because as the
eld was increased the system became more non-linear (n o 1).
This reects the fact that the systems were quite affected by the
eld, and the lower values of n, coupled with higher values of 0
and k imply that the ferrouid based system was affected more
strongly. So this should have better application potential in real
life use.

1000
0 kOe
3.6 kOe
6.7 kOe

0 kOe
3.6 kOe
6.7 kOe

200

400

800

Shear stress, (Pa)

counterparts were also observed as (1 0 0) peak of hcp Co

appeared in x-ray diffraction pattern of NiCoJeffamine. The
morphology of as-prepared NiCo ower-like nanostructure in
presence of Jeffamine were analyzed using low-magnication
eld-emission scanning electron microscopy (FESEM, Quanta
FEG, FEI) images as shown in Fig. 2. The structural evolution of
rose-like nanoower for NiCoJeffamine was studied analyzing
particles in FESEM at various time intervals (Fig. 2ac). At early
stage of reaction, the sample was composed of spherical nanoparticle of about
450 nm in size with smooth surface (Fig. 2a). As
the reux time increased to 90 min, tiny ridges of sheets were
observed on the surface and the size of particle was increased to

650 nm. At nal stage (after 3 h), nanosheets grew larger to form
rose-like nanostructures of
700 nm in size (Fig. 2c). The typical
thickness of nanosheets was about 30 nm and was connected to
each other through the core. TEM image (using Technai F20s, FEI)
of single nanoower shown in Fig. 2 further revealed the interplanar lattice spacing of 0.205 nm, corresponding to (1 1 1) plane
of cubic (fcc) NiCo crystals. Selected area diffraction (SAED) for the
marked region indicated polycrystallinity in sample. Although the
detailed mechanism of growth is unknown, it was experimentally
observed that triblock copolymer helped directing anisotropic
growth towards the preferential plane to form ower-like nanostructures. From HRTEM and SAED, it was shown that the
preferential growth direction for 2D nanosheets of NiCoJeffamine
nanoower was along (1 1 1) plane. EDX analysis conrmed the
composition of the sample and it was shown that nal composition (Ni51Co49) varied only slightly from initial molar composition (1:1) of respective metal salts. However, it can be noted
that concentration of triblock copolymer, pH of reacting media
and appropriate molar ratios of Ni and Co-salts in precursor
were equally signicant in determining the nal morphology of
nanoower.
The magnetic properties of as-prepared NiCo nanostructures
with an average diameter of 700 nm were investigated at room
temperature vibrating sample magnetometric (VSM) studies using
Lakeshore Cryotronics Inc. model 7400s VSM. The hysteresis loop
and ZFC-FC curve at 50 Oe eld were shown in Fig. 3. The
saturation magnetization (Ms) and coercivity (Hc) was calculated
as 108.6 emu/g and 78.4 Oe, respectively. It was observed that the
value of Ms was close to that of bulk alloy with 1:1 composition.
The magnetization curve shows a blocking type behavior, with a

75

600

400

200

Coercivity, Hc = 78.4 Oe

FC

Remanence, Mr = 14.3 emu/g

Saturation magnetization, Ms = 108.6 emu/g

ZFC
8

M (emu/g)

Magnetization, M (emu/g)

12

-20

-10

10

Samples

Field (kOe)

0 (Pa)

k (Pa sn)

MR1

0
3.6
6.7


18.7
52.6


3.19
4.09


0.581
0.584

MR2

0
3.6
6.7


350.8
552.8


13.48
14.97


0.453
0.431

-100

100

1000

Table 1
Fitting parameters to the HerschelBulkley model. Note that the zero eld ts were
rather poor and the t values were unphysical.

20

Field (kOe)

800

-1
Shear rate, d /dt (s )
Fig. 4. Steady state magnetorheological results for MR1 (NiCo nanoower dispersed in silicone oil, closed symbol) and MR2 (NiCo nanoower dispersed in
ferrouid, open symbol) under different magnetic elds.

100

600

200

300

Temperature, T (K)
Fig. 3. Room temperature ZFCFC curve of Jeffamine containing Ni51Co49 nanoowers recorded at 50 Oe. In inset, room temperature magnetic hysteresis (MH) of
the sample (bottom).

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I. Arief, P.K. Mukhopadhyay / Physica B 448 (2014) 7376

5. Conclusion

References

In this communication, we showed that we could prepare a

nanoower like structure of NiCo alloy particles composed of
2D-nanosheets with the help of Jeffamine polymer. We characterized it, and showed that it can be made practically useful in
magnetorheological applications.

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Acknowledgments
One of the authors, IA, thanks Council of Scientic and Industrial
Research (CSIR), India for the award of JRFSRF fellowships.