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Physica B
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art ic l e i nf o
a b s t r a c t
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
2. Experimental method
n
http://dx.doi.org/10.1016/j.physb.2014.04.068
0921-4526/& 2014 Elsevier B.V. All rights reserved.
74
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)
(220)
(200)
40
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.
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.
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
75
600
400
200
Coercivity, Hc = 78.4 Oe
FC
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).
76
5. Conclusion
References
Acknowledgments
One of the authors, IA, thanks Council of Scientic and Industrial
Research (CSIR), India for the award of JRFSRF fellowships.