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Journal of Magnetism and Magnetic Materials 226}230 (2001) 1915}1917

Magnetic properties of FePt /Au and CoPt /Au core-shell


V V
nanoparticles
Charles J. O'Connor*, Jessica A. Sims, Amar Kumbhar,
Vladimir L. Kolesnichenko, Weilie L. Zhou, Joan A. Wiemann
Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148, USA

Abstract

The gold-coated nanocomposites with magnetic core based on the alloys FePt, Fe Pt, CoPt and CoPt were
 
synthesized using the reverse micelles technique. They were characterized using X-ray di!ractometry, SQUID mag-
netometry and electron microscopy (TEM). It was found that the Fe Pt/Au samples exhibited higher coercivity than

FePt/Au, 2885 Oe vs. 500 Oe at 2 K. For the cobalt-based materials, the values of blocking temperature and coercivity
increase as the Pt content increases. Annealing of the Co/Au and CoPt /Au composites at 4003C did not cause any

signi"cant change in the magnetic behavior. Annealing of FePt/Au and CoPt/Au samples caused increase of coercivity,
H "194 vs. 0 Oe for the former, and H "500 Oe vs. 25 Oe for the later composite at 300 K. We suppose that annealing
! !
of both 1 : 1 alloys caused ordering in their cores, that a!ected their magnetic properties.  2001 Elsevier Science B.V.
All rights reserved.

Keywords: Nanoparticles; Transition metal; Ferromagnetic materials; Composites

1. Introduction n-octane and n-butanol from Aldrich, chloroform and


methanol from EM Scienti"c and CoCl ) 6H O (99.9%)
 
Iron/platinum and cobalt/platinum alloys exhibit en- from Alfa Aesar, were used as received.
hanced ferromagnetic behavior as compared to pure Fe or All syntheses were performed in argon using a Schlenk
Co [1]. Dimensional reduction to nanoscale, makes these technique. Microemulsion systems consisted of an oil-
alloys very useful in the design of novel storage media. phase octane, surfactant CTAB, co-surfactant BuOH and
A reverse micelles technique has proven to be a su$cient an aqueous phase containing the reactants (for "16,
synthesis method for fabricating nanosize disordered the weight ratio, respectively: 12 : 6 : 5 : 5). Initially, two
metal alloys. Heat treatment of disordered FePt alloys such solutions were prepared: one with metal salts
increase the degree of long-range order in the cores, which (0.425 mmol per 2.5 g of aqueous solution) and another
decreases the antiferromagnetic interactions between with reducing agent NaBH (2.9 mmol per 2.5 g of aque-

Fe}Fe pairs [1}3]. Here, we present the results of a study ous solution). Then both solutions were mixed and stir-
of core/shell nanocomposite alloys and demonstrate the red for 2 h [4,5]. Excess of borohydride was used to
e!ect of thermal treatment on their magnetic properties. suppress oxidation of Fe and Co by water. Then, the
micelles were expanded to accommodate a passivating
gold shell by reducing 0.06 M aqueous gold salt. The
2. Experiment
magnetic particles were isolated using magnetic "eld,
washing with chloroform/methanol (1 : 1) and drying in
Chemicals: FeSO ) 7H O, PtCl , HAuCl ) 3H O,
     vacuum. Some solids were annealed at 4003C for 4 h
cetyltrimethylammonium bromide (CTAB), NaBH ,
 under argon.
The crystallite size and structure was analyzed
* Corresponding author. Fax: #1 504-280-3185. by a Phillips-X'PERT X-ray di!ractometer with a scintil-
E-mail address: cjoconno@uno.edu (C.J. O' Connor). lation detector. Electron microscopy (TEM), EDS and

0304-8853/01/$ - see front matter  2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 8 8 5 3 ( 0 0 ) 0 0 6 6 1 - 2
1916 C.J. O+Connor et al. / Journal of Magnetism and Magnetic Materials 226}230 (2001) 1915}1917

SAD were preformed on a JEOL 2010. Magnetic Table 2


measurements were done using MPMS SQUID mag- Summary of magnetic data for CoPt /Au alloys
V
netometer.
Parameter Co/Au CoPt/Au CoPt /Au


3. Results and discussion ¹ (K) at 100 Oe 60 80 106


H (Oe) at 10 K 20 200 415
!
XRD demonstrated that both FePt and Fe Pt have

FCT crystal structures, which agrees with published data
[1,6]. Gold peaks were also observed. The crystallite size Table 3
ranged from 6 to 20 nm for the 2 : 1 alloy and the 1 : 1 Magnetic properties of the annealed and unannealed CoPt/Au
alloy, respectively. TEM images showed isolated spheri- samples
cal core-shell structures (3 to 5 nm) with a uniform size
distribution of less than 10%. Also, TEM and SAD Parameter CoPt/Au CoPt/Au
demonstrated well-de"ned single crystals as compared to unannealed annealed
particles from unannealed FePt samples. EDS has detec-
2 K hysteresis (Oe) 375 720
ted Fe, Pt and Au in the specimens. 10 K hysteresis (Oe) 200 645
TEM for CoPt shows that particle sizes are &15 nm
 300 K hysteresis (Oe) 25 500
with a size distribution of less than 10%. EDS show the
presence of 16.2 wt% of Pt, 52.5 wt% of Co and 31.3 wt%
of Au. In the XRD plot, characteristic peaks of Au, Co,
CoPt and CoPt appear in their respective samples. The

average crystallite size is &15 nm using Sherrer formula
and comparing the full-width at half-maximum (FWHM)
of the most intense peak of the sample to an internal
reference standard.

Table 1
Summary of magnetic data for FePt /Au alloys
V
Parameter FePt/Au FePt/Au Fe Pt/Au

unannealed annealed unannealed

¹ (K) at 100 Oe 70 300 53


M (emu/g) at 10 K 2.3 18 1.6
0
H (Oe) at 2 K 500 1912 2885
! Fig. 2. Hysteresis loop for the annealed CoPt/Au, 300 K.
H (Oe) at 10 K 500 1032 2013
!
H (Oe) at 300 K 0 194 0
!
Magnetic properties of FePt/Au and Fe Pt/Au are

summarized in Table 1. Both are superparamagnetic
below the blocking temperature, ¹ "70 K for the for-
mer and 53 K for the later. The Fe Pt/Au samples exhib-

ited higher coercivity than FePt/Au, 2885 Oe vs. 500 Oe
at 2 K. Annealing of the FePt/Au composite at 4003C
leads to the higher coercivities of 1912 Oe at 2 K and
194 Oe at 300 K (Fig. 1).
Magnetic properties of cobalt-based materials are
summarized in Table 2. The values of both blocking
temperature and coercivity increase as the Pt content
increases. Annealing of the Co/Au and CoPt /Au com-

posites at 4003C did not cause any signi"cant change in
the magnetic behavior. In contrast, the CoPt/Au samples
showed an increase in coercivity (Table 3), which is espe-
cially noticeable at higher temperature: H "500 Oe vs.
!
25 Oe at 300 K (Fig. 2). We suppose that the observed
Fig. 1. Hysteresis loop for the annealed FePt/Au, 300 K. e!ect of annealing on the magnetic properties for both
C.J. O+Connor et al. / Journal of Magnetism and Magnetic Materials 226}230 (2001) 1915}1917 1917

1 : 1 alloys, FePt/Au and CoPt/Au, is caused by ordering [3] T. Sasaki, S. Chikazumi, J. Phys. Soc. Japan 46 (6) (1979)
in their cores. 1732.
[4] E.E. Carpenter, J.A. Sims et al., J. Appl. Phys. 87 (2000)
5615.
Acknowledgements [5] E.E. Carpenter, C.T. Seip, C.J. O'Connor, J. Appl. Phys. 85
(1999) 5184.
[6] Reference X-ray Powder Di!raction Patterns, International
This work was supported by the Advanced Materials Center for Di!raction Data, Newtown Square, PA, 1996.
Research Institute, through DARPA Grant No.
MDA972-97-1-0003.

References

[1] J.W. Bowles, Mineral. Petrol. 43 (1990) 37.


[2] L. Benner, S. Meguro, Precious Metals Science and Techno-
logy, The International Precious Metal Institute, 1991,
(Chapter 3).