Sei sulla pagina 1di 7

Journal of Magnetism and Magnetic Materials ()

1 Contents lists available at ScienceDirect

4 Journal of Magnetism and Magnetic Materials
journal homepage:
Low temperature FMR investigations on double surfactant water based
13 ferrouid
Q1 A. Shankar a,b, M. Chand a, G.A. Basheed a, S. Thakur b, R.P. Pant a,n
17 EPR Spectroscopy Section, CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi 110012, India
School of Applied Sciences, Netaji Subhas Institute of Technology, University of Delhi, Sector 3, Dwarka, New Delhi 110078, India
21 art ic l e i nf o a b s t r a c t
Article history: Magnetite nanoparticles were synthesized by coprecipitation of reverse micelles in an aqueous phase.
Received 24 June 2013 XRD, TEM and VSM results conrm the average particle size 910 nm. The FMR measurements were
24 Received in revised form performed in zero-eld-cooled (ZFC) and eld-cooled (FC) protocol. Raikher and Morais models were
25 10 September 2014
used for interpreting the resonance eld and linewidth results. A value of 2.3  10  2 erg cm  2 for
26 intrinsic surface anisotropy constant is observed as per the Raikher model. The higher melting point of
27 Keywords: water leaves the magnetic particles with a more disordered distribution of anisotropy axes of particles
28 Ferrouid even in FC measurements. The angular variation of resonance eld differentiates the magnetic behavior
29 Ferromagnetic resonance of system in 440 K (region I), 70200 K (region II) and 200260 K (region III). The value of effective
Spin-glass transition
30 magnetic anisotropy constant varied from 4.7  104, 2.1  104 to 0 erg cm  3 through regions I, II to III.
31 Linewidth analysis reveals that system undergoes spin-glass transition 46 K. The tting of linewidth
32 data for region I and II indicate the presence of frozen and unfrozen surface spin states. Moreover, the
33 role of applied magnetic eld i.e. 1 T in eld-cooled FMR spectra is reected in interparticle distance
parameter and magnitude of energy barriers related to the relaxation mechanisms. At 260 K uid melts
resulting in minimization of angular dependent anisotropy in resonance lines.
& 2014 Published by Elsevier B.V.
1. Introduction temperature determinative for this dynamic phase transition is 69
regarded as blocking temperature, TB. 70
Ferrouids (FFs) are an important class of magnetic materials In addition, the reduced lattice symmetry of atoms on the 71
surface of MNPs gives rise to a disordered surface layer also 72
43 since they have found numerous technological applications. Their
termed as dead layer, which is antiferromagnetic in nature. 73
44 peculiar properties such as superparamagnetism, dipolar interac-
The lower value of saturation magnetization in MNPs has been 74
45 tions, blocking of moments by anisotropy eld and effects of
ascribed to the presence of this non-magnetic surface layer [8]. 75
46 different carrier medium offers intensive research opportunities
This further adds another dimension of complexity when one 76
47 [1]. Among these, superparamagnetic relaxation of magnetic
assumes a coreshell kind of structure in individual MNPs. This 77
48 moments in these nanoparticles resulting from magnetization
structural perspective becomes more evident especially below 78
reversal is an important aspect for majority of their applications. 79
50 surface spin-freezing temperature [913]. Below this characteristic
Thus, they have been widely studied by a variety of techniques temperature, a coupling of uniaxial FM core and surface spin glass 80
having quite different time scale of measurements (M) viz., DC generates a non-zero exchange anisotropy eld in system. 81
susceptibility measurements (1100 s) and low-frequency AC To study spin dynamics in such a system, the FMR technique 82
susceptibility measurements (10  110  5 s), Mossbauer spectro- has been utilized in many instances. A classical ferromagnetic 83
scopy (10  710  9 s) and ferromagnetic resonance (FMR) with approach using the LandauLifshitzGilbert equation incorporated 84
56 M 10  10 s [27]. But, the uctuation of magnetic moments stops with thermal parameters is widely used to understand dynamics
of uctuating moments in these systems [5,1416]. An alternative 86
57 when magnetic anisotropy energy dominates over thermal energy
method to the above approach is proposed by Noginova et al. [17] 87
58 of magnetic nanoparticles (MNPs) and system becomes single-
where iron oxide MNPs were considered as a giant macrospin 88
59 domain ferromagnetic (bulk-like) in nature, and the critical
under quantization model to describe spectral linewidth, reso- 89
nance condition and signal intensity. On the other hand, FMR has 90
n also been used to study spin-glass transition in mixed and doped 91
62 Corresponding author. Fax: 91 11 4560 9310.
E-mail address: (R.P. Pant). iron oxide nanoparticles [10,1820]. A sudden decrement in 92
64 94
65 0304-8853/& 2014 Published by Elsevier B.V. 95

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),
2 A. Shankar et al. / Journal of Magnetism and Magnetic Materials ()

1 resonance eld and a simultaneous enhancement in spectral 67

2 linewidth respectively with the decrease in temperature are 68
3 accompanied by this characteristic transition. 69
4 The aim of this work is to describe experimentally observed 70
5 spin-glass transition using the Raikher and Morais models [2127]. 71
6 Later on, freezing effects of carrier medium in double surfactant 72
7 water based ferrouid were also observed. The particles were 73
8 prepared by reverse micelle precipitation in aqueous phase and 74
9 coated twice with oleate group, each in a reverse manner for a 75
10 good dispersion in water. The FMR investigations of water based FF 76
11 are seldom reported due to high microwave absorption tendency 77
12 of water. The aqueous dispersions similar to this double surfactant 78
13 FF are used very frequently in biomedical applications [28]. 79
14 80
15 81
16 2. Synthesis and experimental methods 82
17 83
18 The Fe3O4 nanoparticles (FNPs) were synthesized in two steps 84
19 via chemical route. In rst stage, 13.96 g FeSO4  7H2O and 16.21 g 85
20 FeCl3 were dissolved in 100 mL MilliQ water along with 4 mL oleic Fig. 1. Room temperature X-ray diffraction pattern of Fe3O4 nanoparticles with
21 acid. The mixture was ultrasonicated with 2 mL acetone as Rietveld renement. (a) TEM micrograph of as synthesized FNPs. (b) Magnetization 87
22 emulsier for 25 min to form oil-in-water emulsion. It was then curve with t with a comparison of particle size distribution from VSM and TEM 88
23 results. 89
heated to 70 C followed by addition of 60 mL of 25% aq. NH3 in a
24 time span of 35 min. The mixture was subsequently cooled down 90
25 and magnetically separated for washing by MilliQ water. In second shaped particles can be described by following equation [20,30]: 91
26 stage, a 20 mL aqueous solution of sodium oleate (3.8580 g) was 92

prepared by heating at 50 C (15 min). The washed precipitate was M= 0 L () f (D) dD i H
28 94
transferred to above solution and heated for further 15 min. The
mixture was allowed to cool down and centrifuged at 13,500 rpm where L() is the Langevin function, 95
30 96
for 15 min. The ltrate was separated via pipette and labeled as FF.
The structural characterization was performed by a Rigaku
L () = Msf coth () ; Msf = Md with =
Md H (1/6) D3 ( ) 97
32 kT 98
powder X-ray diffractometer with Cu-K radiation, 40 kV A and
33 99
30 mA with step size 0.02/s, scan range (2) from 25 to 80. The and f (D) is the log-normal size distribution of MNPs
34 100
morphology of nanoparticles was examined with M/s Tecnai F30
35 1 101
HRTEM. The magnetization measurements were carried out on f (D ) = e { ln (D / Do )2 /2 D2 }
36 2 D D 102
these samples using were carried out using vibrating sample
37 103
magnetometer (VSM) model 7304 from Lakeshore Cryotronics Here, sD is the standard deviation, H is the applied magnetic
38 104
Inc., USA. The ferromagnetic resonance (FMR) measurements were eld, k is the Boltzmann constant, T is the temperature, Msf is the
39 105
performed using a M/s Bruker biospin (model A300) using uid magnetization, is the solid volume fraction of FNPs in the 106
rectangular resonator cavity having TE102 resonance mode in the FF, Md is domain magnetization, Do is median diameter and iH 107
temperature range 4300 K. Before low temperature measure- represents diamagnetic contribution from surfactants and water in
42 108
ments, the signal channel was calibrated at room temperature sample.
43 109
using 1 mg DPPH standard. The best t of Eq. (1) to the MH curve (shown in inset (b)) is
44 110
45 obtained for Do 9.6(2) nm, Md 3.84  105 A m  1 384 G with s 111
46 D 0.23, Ms 1.0(1) emu/g and 0.0129. Further, to estimate 112
47 3. Results and discussion particle concentration (n), the volume fraction can be expressed 113
48 as 114
49 3.1. Structural characterization 115
50 = n Do3 116
6 (2)
51 The Rietveld renement of the XRD pattern (Fig. 1) of FNPs was 117
52 performed by the use of FullProf via pseudo-voigt prole method. Using requisite values in Eq. (2) the particle concentration for 118
53 Using the WilliamsonHall equation [29], the calculated average the present sample was found as 2.78  1022/m3. Further, while 119
54 crystallite size (D) and strain () induced in the FNPs were found to assuming that particles are uniformly distributed in the uid, the 120
55 be 9.8(1) nm and 0.0010(1) respectively. The inset in Fig. 1 average core-to-core interparticle distance can be calculated by 121
56 (a) shows the morphological view of the NPs. The average particle (1/n)1/3, which is 32.9 nm. 122
57 size was calculated by counting over 150 NPs, and found to be 123
58 10.9 nm with standard deviation, s 2.8 nm. 3.3. FMR measurement 124
59 125
60 3.2. Magnetic measurement FMR measurements were performed on ten times diluted FF 126
61 sample kept in a ne cylindrical quartz capillary. Thus, average 127
62 The magnetization curve of FF recorded at room temperature is interparticle distance is now 71.1 nm. A typical FMR spectra at 128
63 shown in Fig. 1 (inset (b)). The MH loop showed a low coercive room temperature constitutes a broad ferrimagnetic signal 129
64 eld of 2.5 Oe which indicated that particles exhibit superpara-  3100 Oe superimposed by a sharp signal at  3400 Oe due to a 130
65 magnetic nature. Further while assuming the non-interacting superparamagnetic phase which is similar to the previous reports 131
66 behavior, the magnetic state of such a system with spherical [25,31]. The low temperature FMR measurements were performed 132

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),
A. Shankar et al. / Journal of Magnetism and Magnetic Materials () 3

1 onwards. In later part this has been ascribed to the surface spin- 67
2 glass transition taking place due to freezing of surface spins (Fig. 3 68
3 (c)). Region II (50 Ko To200 K) shows the core dominant feature 69
4 i.e. ferromagnetic behavior of FNPs. In region III 70
5 (200 K oT o300 K) the resonance lines gradually loses their 71
6 angular anisotropy with progressive increase in temperature and 72
7 becomes unobservable when uid melts. 73
8 In FC measurements, the applied eld of 1 T is chosen inten- 74
9 tionally so as to create the environment where Hcf c HA, HA is 75
10 anisotropy eld [20,25,33]. This condition works in the favor of 76
11 minimizing orientational distribution of anisotropy axes for 77
12 achieving an excellent texturation in the sample. For the ZFC 78
13 sample having random distribution of anisotropy axes, the reso- 79
14 nance eld of a particle with uniaxial anisotropy is given by 80
15 [24,34] 81
16 82
17 HR = HA (P2 cos ) 83
18 84
19 where, P2 is Legendre polynomial. For perfectly aligned particles, 85
20 the resonance eld in parallel and perpendicular orientation, i.e. 86
21 for 0 and 90, can be written as HR(0) o/  HA and HR(90) 87
22 Fig. 2. Selected ZFC and FC recorded spectra for FF. o/ HA/2. The simplication yields HR(90)  HR(0) (3/2)HA. 88
23 Using values from Fig. 3(a), one nds HA Z340 Oe. The equality 89
24 in two different protocols; zero-eld cooled (ZFC) and eld-cooled is valid for an ideal frozen ferrouid where there is a perfect 90
25 (FC) to investigate the spin dynamics of the system. Fig. 2 shows texturation. However during preparation of real eld frozen 91
26 selected FMR spectra recorded via ZFC and FC procedure with a ferrouid samples, thermal energy tries to disorient the magnetic 92
27 dened 3-dimensional coordinate axis system of FNPs under moments which in turn are bounded to the anisotropy axes of 93
28 study. particle. This affair always results in a nite amount of orienta- 94
29 These measurements were carried out using 9.54 GHz micro- tional disorder affecting the alignment of anisotropy axes in real 95
30 wave frequency with the power of 1.03 mW [32]. Thus reference cases [25,35]. The magnitude of Hcf is one the factors which affects 96
31 resonance eld set for these measurements is o/ 3.404 kOe, this orientational distribution and hence 1 T of eld is chosen 97
32 where is gyromagnetic ratio of free electrons. A 100 kHz intentionally to minimize this effect. 98
33 modulation frequency and 6 G of modulation amplitude was used From Fig. 3(a) it is clear that ZFC and FC resonance lines shifts 99
34 for recording spectra. In ZFC measurements, the sample was isotropically away from reference eld for T o200 K. This behavior 100
35 cooled down from 298 K to 4 K in zero magnetic eld and the has been proposed to have surface origin which has been well 101
36 spectra were recorded while raising the temperature. For the FC conrmed by many researchers [19,20,25]. This isotropic shift is 102
37 measurements, the sample was cooled in magnetic eld (Hcf) of dened by Hiso o/  HR(ZFC), where the shift can be seen as an 103
38 extra unidirectional internal eld always parallel to the magnetiz- 104
1 T to form textured suspension and spectra were recorded during
39 ing eld. The strength of this uniform intrinsic eld is greater for 105
warm up cycle (4298 K) at different angular orientations (i.e. 0,
40 smaller sized particles. Raikher and coworkers extended this FMR 106
30, 60, 90, 120, 150, and 180) at each specied temperature.
41 107
Fig. 3(a) shows variation of resonance eld (HR) in the temperature theory of MNPs where they assumed that at low temperatures the
42 108
range from 4 K to 298 K for ZFC and FC measurements. magnetization is weakly pinned at the particle surface by a
43 109
In ZFC, resonance eld shows a non-monotonic behavior with a unidirectional anisotropy [26]. Under the condition of a weak
44 110
maximum at 200 K. The corresponding FC data with in plane surface pinning, a uniform external radio-frequency eld instead
45 111
angular rotation also retained this behavior but reveal more of the uniform Larmor precession excites in a particle a magneti-
46 112
interesting features. For simplicity we have divided Fig. 3(a) into zation mode that is spatially modulated along the radius. Thus, the
47 113
three regions. Region I shows the temperature region resonance eld value for a single particle can be expressed as a
48 114
(4 KoT o50 K) where a steep rise in HR can be seen from 40 K combination of an internal surface and bulk anisotropy elds as
49 115
50 116
51 117
52 118
53 119
54 120
55 121
56 122
57 123
58 124
59 125
60 126
61 127
62 128
63 129
64 130
65 131
66 Fig. 3. (a) HR vs T for ZFC and FC measurements (4298 K). (b) Variation of isotropic shift and 2/3[HR(90)  HR(0)] with temperature. 132

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),
4 A. Shankar et al. / Journal of Magnetism and Magnetic Materials ()

1 follows: textured form. Thus, one needs to consider the magnitude of this 67
2 disorder in calculation. In addition, the usage of Eqs. (6)(8) for 68
o 6KS
3 HR () = Ha (P2 cos ) determining KS has been found reliable but the same is not true for 69
ID (4)
4 Ha [25,27]. 70
5 where, I is the magnetization of dispersed MNPs, D is the particle Fig. 4 shows angular variation of FC resonance eld values. The 71
6 diameter, Ha is the bulk anisotropy eld, KS is effective intrinsic characteristic behavior of resonance eld values with maxima 72
7 anisotropy constant due to surface anisotropy, is the angle around 90 and minima around 0 and 180 proves that particles 73
8 between n^ and applied sweeping eld and P2 is associated have uniaxial kind of anisotropy [17,20,25,33]. To explain angular 74
9 Legendre polynomial. For ZFC samples, the isotropic angular variation of three different regions we use model developed by 75
10 averaging of the pertinent uniaxial anisotropy is valid and hence Morais and coworkers [22,23]. In this model, the effective mag- 76
11 an angular independent relation can be written as netic eld (HEFF) acting on MNPs at resonance condition is 77
12 proposed to constitute three main components, viz., external 78
13 o 6KS 79
Hiso = HR (ZFC) = sweeping eld (HE), exchange anisotropy eld (HX), and effective
14 DI (5) 80
uniaxial anisotropy eld (HEK). At resonance, the external eld
15 81
Fig. 3(b) shows the variation of Hiso with temperature. Using becomes equal to resonance eld and the resonance condition can
16 82
I 384 G and D 9.6 nm, one obtains KS 2.3  10  2 erg cm  2 at be expressed mathematically as follows:
17 83
4 K, which is consistent with other reports [25,26]. For a textured
18 HR = HEFF HX HEK (9) 84
suspension, Eq. (5) can be further resolved for two general cases,
19 85
20 where the orientation of anisotropy axis to the external eld can with, HEK = (KEFF/I)(3 cos2 1) and KEFF = K V + (6/D) KS where, KV 86
21 be parallel or perpendicular whose resonance conditions can be and KS both are anisotropy constants having volume and surface 87
22 written as origin respectively [36]. Employing Eq. (9) and using I 384 G the 88
23 theoretical t is performed on the experimental data in order to 89
o 6KS
24 HR (0) = Ha obtain effective magnetic anisotropy of particles. The KEFF values 90
DI (6) obtained after tting angular variation data of Fig. 4 is shown in
25 91
26 and Fig. 5. The behavior of magnetic anisotropy shows that its 92
27 magnitude decreases with increase in temperature, which is 93
o 3KS H consistent with previous reports [22]. Though, effective anisotropy
28 HR (90) = + + a 94
DI 2 (7) in lowest temperature regime (region I; 440 K) is highest, but is
29 95
30 still smaller than the bulk value of Fe3O4 i.e. 1.1  105 erg cm  3 96
Simplifying Eqs. (6) and (7), one obtains
31 [37]. This observation is directly related to the nite size effects 97
32 2 6KS and larger interparticle distances in the matrix. It should be 98
[HR (90) HR (0)] = + Ha
3 DI (8) remarked that the thermal variation of effective anisotropy is
33 99
34 clearly visible in Fig. 5 with three distinct regions, as already 100
By using observed resonance eld values in left hand side of Eq.
35 marked in Fig. 3(a). The red lines are the linear ts to different 101
(8), the thermal variation of the same is plotted in Fig. 3(b). regions. The extrapolation of linear t to the y-axis, where (1000/
36 Though if one uses Eqs. (5) and (8), to determine Ha, then one can 102
37 T)-0, yields characteristic value of KEFF for the corresponding 103
observe positive and negative values at different temperatures. region. For regions I and II, the KEFF values are 4.7  104 and 2.1 
38 104
This can be further explained as follows. As discussed above, in a 104 erg cm  3 respectively, whereas region III shows its value near 105
magnetic uid there is no opportunity to achieve a perfect to zero due to melting of carrier liquid. Here, it is conspicuous that
40 106
texturation. In fact, the carrier medium employed here, i.e. water the rise in KEFF is more than 50% from regions II to I. Though KEFF is
41 107
freezes around 260 K, which is high enough so that a good amount combination of both volume and surface terms but we relate such
42 108
43 of orientational disorder of anisotropy axes is present in the an enhancement to the dominance of surface effects present at 109
44 110
45 111
46 112
47 113
48 114
49 115
50 116
51 117
52 118
53 119
54 120
55 121
56 122
57 123
58 124
59 125
60 126
61 127
62 128
63 129
64 130
65 131
66 Fig. 4. HR vs T for FC measurements (a) 440 K and (b) 70270 K. Solid lines are t to Eq. (9). 132

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),
A. Shankar et al. / Journal of Magnetism and Magnetic Materials () 5

1 67
2 68
3 69
4 70
5 71
6 72
7 73
8 74
9 75
10 76
11 77
12 78
13 79
14 80
15 81
16 82
17 83
18 84
19 85
20 86
Fig. 5. Thermal variation of effective magnetic anisotropy energy constant. Inset
21 Q2 87
shows the schematic diagram of a nanoparticle with frozen surface spin state. (For
22 interpretation of the references to colour in this gure legend, the reader is referred 88
23 to the web version of this article.) 89
24 90
25 91
26 nanometer scale where contributions from volume are negligible. Fig. 6. (a) ZFC, (b) FC || and (c) FC linewidth data with complete region t. (d) FC 92
27 At lower temperatures, the MNPs are proposed to have a core- , (e) FC || and (f) ZFC linewidth data with two-region t. Green region shows the 93
28 temperature region where the onset of freezing of surface spins takes place. (For 94
shell structure whose surface spins freeze at a characteristic interpretation of the references to colour in this gure legend, the reader is referred
29 temperature called surface spin-glass transition temperature 95
to the web version of this article.)
30 (TSG) [19,20,3840]. In FC protocol, the surface spins freeze in 96
31 the direction of Hcf below this characteristic temperature. Before 97
32 linewidth behavior in different MNP systems [39,47,48]. According 98
recording FC spectra when Hcf is removed, the core experiences a to the model, line broadening can be described by
33 nite amount of magnetic eld generated intrinsically by eld 99
34 frozen surface spins which in turn further enhances the anisotropy E 100
35 Hpp = L tanh
of system in T oTSG temperature region. When T 4TSG, aligned 2kT (10)
36 frozen surface spins melts and anisotropy is observed alone due to 102
37 with E = EA + Emd + EH + EB + EC + Eed and 103
ordered ferromagnetic core in the system (region II;
38 70oT o200 K). Perhaps, this freezing of surface spins could be 5gSn 104
39 L= 105
the probable cause for the system to exhibit a slight deviation from R3
40 uniaxial anisotropy in region I (Fig. 4(a)). However, using current 106
41 model on ZFC and FC spectra, an exact estimate of surface and where, g is the g-factor, is the Bohr magneton, S is the effective 107
42 exchange anisotropy is possible if one performs measurements on spin of magnetic center, n is the number of magnetic centers inside 108
43 variable sized particles [23]. each grain, R is the average interparticle distance, E is the energy 109
44 In region III at 260 K, the effective magnetic anisotropy gets barrier through which MNPs relaxes, EA is the magnetocrystalline 110
45 minimized with the evolution of a small peak around 3400 Oe anisotropy energy term, Emd is the magnetic dipoledipole inter- 111
46 action, EH is the interaction between moment of particle and 112
along with earlier broad FMR signal. At 265 K and 270 K, the
47 external eld, EB represents the Brownian motion energy, EC is the 113
intensity of this small peak is enhanced without angular depen-
48 electrical Coulomb energy, Eed is the electric dipole energy, k is the 114
dency of main FMR signal. We explained this as the melting of
49 Boltzmann constant and T is temperature. 115
carrier liquid  260 K which rather facilitates the physical rotation
50 The pre-factor, L is related to the magnetic moment of particles 116
of FNPs via Brownian relaxation process in a liquid state. This
51 and their average interparticle distance. Thus, L is a parameter 117
relaxation process is well known to result in insensitivity of
52 which depends upon the sample under investigation. In frozen 118
resonance with respect to angular rotations. The choice of water
53 ferrouids, the reorientational mechanism of particle magnetic 119
54 as a carrier medium offers a higher melting stage (273 K for water) moments via Brownian relaxation is infeasible. Moreover, by 120
55 to the uid but a current depression in melting point (i.e.  260 K) ignoring the weaker electrical contributions in such uids, the 121
56 can be explained by colligative properties of solutions, since the FF expression describing energy barrier reduces to E EA Emd EH 122
57 under study is a many component system comprising FNPs, free [43]. 123
58 ions (Fe2 /3 , Na etc.), free surfactants in water. The complete range of linewidth data of ZFC and FC (|| and ) 124
59 Fig. 6 shows variation of peak-to-peak linewidth (Hpp) with i.e. 4 KoT o300 K does not yield a good t to Eq. (6); especially 125
60 temperature for ZFC, || and ongurations. However, Hpp does for T o100 K, as can be seen in Fig. 6(a)(c). Thus, it again seems 126
61 not show any signicant angular variation in FC measurements that it is a crossover of two regions i.e. I and II. This further point 127
62 which is consistent with other reports [25,41]. Instead, a consis- towards the occurrence of a magnetic phase transition in the 128
63 tent temperature dependent decrease is observed for both ZFC and system. Recently, Upadhyay et al. [39] observed similar linewidth 129
64 FC measurements. Such behavior of Hpp in MNPs can be well behavior in Gd3 doped Mn0.5Zn0.5Fe2O4 due to surface anisotropy 130
65 described by the model developed by Morais and coworkers effects. Thus, in view of above points, we divided the linewidth 131
66 [21,4246]. The same has been successfully utilized for describing data in further two parts viz., To 50 K and T 450 K for tting Eq. 132

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),
6 A. Shankar et al. / Journal of Magnetism and Magnetic Materials ()

1 Table 1 Fe3O4 nanoparticles of  10 nm size. The sizes obtained from XRD, 67

2 Fitted parameters derived from Fig. 6(d)(f). TEM and VSM are in good agreement with each other. The low 68
3 temperature FMR measurements performed in ZFC and FC proto- 69
Measurement type Frozen surface spin state Unfrozen surface spin state
4 (T o 46 K ) (T 446 K) col reveal interesting features. By applying Raikher and Morais 70
5 models, the dominance of surface effects over volume effects is 71
6 L (Oe) E  1021 (J) L (Oe) E  1021 (J) seen in resonance eld behavior. The higher melting stage of 72
7 carrier medium limits the perfect texturation of frozen uid in FC 73
ZFC 1503.7 2.09 1396.4 5.30
8 FC || 1571.7 2.19 1440.9 5.41 measurements. Linewidth analysis using Morais model of FC and 74
9 FC 1629.4 2.12 1491.6 5.38 ZFC spectra gives 46 K as the critical temperature for spin glass 75
10 transition. The formation of chain-like structure and existence of 76
11 surface spin-glass in FC is reected in tted parameters. The 77
12 (10). Thus tting procedure is performed again, but now by energy barrier for relaxation of nanoparticles is different in frozen 78
13 assuming that the system is separated by two different energy and unfrozen surface spin states of magnetic nanoparticles. 79
14 barriers due to frozen and unfrozen surface spin states. The 80
15 parameters L and E obtained after tting are listed in Table 1. 81
16 From Fig. 6(d)(f), it can be seen that the critical temperature for Acknowledgment 82
17 the occurrence of spin-glass transition in our system is around 83
18 46 K, which is well in agreement for similar studied systems This work was supported by Department of Science and Q3
19 [10,19,20,38,39,49]. Technology, Ministry of Science and Technology (DST), Govern- 85
20 In Table 1, it can be seen that the L and E values for both ment of India, (Project no. GAP 123532). Authors would like to
21 regions are greater in FCs as compared to ZFC. This explains the 87
thank Dr. Michael Golosovsky, The Racah Institute of Physics, Israel
22 possible role of Hcf in forming chain-like structure of FNPs in FC 88
for fruitful discussion. One of the authors, A. Shankar is also
23 cases. Thus, interparticle distances will decrease with such mor- 89
thankful to CSIR for his grant of research fellowship (NET). Q4 Q5
24 phological transformation and consequent increments in pre- 90
25 factor L values are observed, since L1/R3. The following calculated 91
26 values gives a further insight to the above raised points. Using 92
27 L 1396.4 Oe, R7.11  10  6 cm, S 4, g 2 and 9.27  References 93
28 10  21 erg G  1, the calculated value of n is found as 1.35  106 for 94
29 [1] R. Taylor, S. Coulombe, T. Otanicar, P. Phelan, A. Gunawan, W. Lv, et al., Small 95
ZFC case when there is no surface spin freezing. Following same
particles, big impacts: A review of the diverse applications of nanouids, J.
30 procedure and using same value of R, the value of n for ZFC in Appl. Phys. 113 (2013) 011301.
31 frozen surface spin state (T o50 K) comes out to be 1.46  106. This [2] T. Wen, W. Liang, K.M. Krishnan, Coupling of blocking and melting in cobalt Q6 97
32 increase in n value can be explained as a result of contribution by ferrouids, J. Appl. Phys. (2010)09B501. 98
[3] M.A. Willard, L.K. Kurihara, E.E. Carpenter, S. Calvin, V.G. Harris, Chemically
33 frozen surface spins. By using n 1.35  106 for FC and in prepared magnetic nanoparticles, Int. Mater. Rev. 49 (2004) 125170. http:
34 T 450 K region, the calculated values of interparticle distance // 100
35 were found as 7.03  10  6 cm and 6.95  10  6 cm respectively, [4] A.J. Rondinone, C. Liu, Z.J. Zhang, Determination of magnetic anisotropy 101
36 distribution and anisotropy constant of manganese spinel ferrite nanoparti- 102
which clearly reects chain formation due to Hcf. Using these
cles, J. Phys. Chem. B. 105 (2001) 79677971.
37 values of R, we calculated the values of n for FC and in T o50 K jp011183u. 103
38 and found 1.52  106 and 1.58  106 respectively. Thus in FC cases [5] K. Usadel, Temperature-dependent dynamical behavior of nanoparticles as 104
39 the freezing of surface spins in direction of Hcf makes surface spins probed by ferromagnetic resonance using LandauLifshitzGilbert dynamics 105
in a classical spin model, Phys. Rev. B 73 (2006) 212405.
40 to contribute more in line broadening. 106
41 Due to close proximities of neighboring particles in chain-like [6] M.M. Noginov, N. Noginova, O. Amponsah, R. Bah, R. Rakhimov, V.A. Atsarkin, 107
42 structures, the contribution from dipole to dipole interaction (Emd) Magnetic resonance in iron oxide nanoparticles: quantum features and effect 108
43 of size, J. Magn. Magn. Mater. 320 (2008) 22282232. 109
will enhance which results in overall enhancement of energy 10.1016/j.jmmm.2008.04.154.
44 barrier in FC cases. One can notice that in region I, the energy [7] P. Allia, P. Tiberto, Dynamic effects of dipolar interactions on the magnetic 110
45 barriers are always lower than in region II irrespective of ZFC and behavior of magnetite nanoparticles, J. Nanoparticle Res. 13 (2011) 72777293. 111
46 112
FCs. Indeed, the linear model proposed here represents a naive
[8] M. Zheng, X.C. Wu, B.S. Zou, Y.J. Wang, Magnetic properties of nanosized
47 approximation, considering three different aspects [43]. First, MnFe2O4 particles, J. Magn. Magn. Mater. 183 (1998) 152156.
48 thermal uctuation of the magnetic moment is not included in [9] R.H. Kodama, A.E. Berkowitz, E.J. McNiff Jr, S. Foner, Surface spin disorder in 114
49 the calculation. Second, there is no consideration of two-dimen- NiFe2O4 nanoparticles, Phys. Rev. Lett. 77 (1996) 394. 115
[10] Y. Koksharov, S. Gubin, I. Kosobudsky, G. Yurkov, D. Pankratov,
50 sional, and three-dimensional particle arrays for its comparison 116
L. Ponomarenko, et al., Electron paramagnetic resonance spectra near the
51 with one-dimensional arrays. Third, there is no parameter in the spin-glass transition in iron oxide nanoparticles, Phys. Rev. B 63 (2000) 117
52 model to account for the effects of frozen/unfrozen surface spin 012407. 118
53 [11] M. Suzuki, S. Fullem, I. Suzuki, L. Wang, C.-J. Zhong, Observation of superspin- 119
states of nanoparticles. Thus, an extension of the Morais model to
glass behavior in Fe3O4 nanoparticles, Phys. Rev. B 79 (2009) 024418. http://dx.
54 these kind of spin-glass states in MNP systems can be checked.
55 Recently, Bakuzis et al. [50] implemented a new three dimensional [12] J. Park, K. An, Y. Hwang, J.-G. Park, H.-J. Noh, J.-Y. Kim, et al., Ultra-large-scale 121
56 polydisperse Monte Carlo simulation approach for describing the syntheses of monodisperse nanocrystals, Nat. Mater. 3 (2004) 891895. http: 122
57 self-organization of nanoparticles in terms of fraction of agglom- 123
[13] M. Sasaki, P. Jnsson, H. Takayama, H. Mamiya, Aging and memory effects in
58 erates, surface-to-surface particle distance within a linear chain superparamagnets and superspin glasses, Phys. Rev. B 71 (2005) 104405. http: 124
59 and agglomerates chain size. Therein the effect of polydispersity // 125
60 [14] E. De Biasi, E. Lima, C.A. Ramos, A. Butera, R.D. Zysler, Effect of thermal 126
as well as short-range interaction in chain formation of particles uctuations in FMR experiments in uniaxial magnetic nanoparticles: blocked
61 along with possible ageing pathways in ferrouids are included. vs. superparamagnetic regimes, J. Magn. Magn. Mater. 326 (2013) 138146.
62 128
63 4. Conclusion [15] A. Sukhov, K.D. Usadel, U. Nowak, Ferromagnetic resonance in an ensemble of 129
nanoparticles with randomly distributed anisotropy axes, J. Magn. Magn.
64 130
Mater. 320 (2008) 3135.
65 In this work we have investigated the chemically synthesized [16] C.A. Ramos, E. De Biasi, R.D. Zysler, E. Vassallo Brigneti, M. Vzquez, Blocking 131
66 water based magnetic uid which constitutes double surfacted effects in magnetic resonance? The ferromagnetic nanowires case, J. Magn. 132

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),
A. Shankar et al. / Journal of Magnetism and Magnetic Materials () 7

1 Magn. Mater. 316 (2007) e63e66. [34] Y.L. Raikher, V.I. Stepanov, The effect of thermal uctuations on the FMR line 44
2 jmmm.2007.02.028. shape in dispersed ferromagnets, Sov. Phys. JETP 75 (1992) 764. 45
[17] N. Noginova, F. Chen, T. Weaver, E.P. Giannelis, A.B. Bourlinos, V.A. Atsarkin, [35] F. Gazeau, V. Shilov, J.C. Bacri, E. Dubois, F. Gendron, R. Perzynski, et al.,
3 Magnetic resonance in nanoparticles: between ferro-and paramagnetism, J. Magnetic resonance of nanoparticles in a ferrouid: evidence of thermouc- 46
4 Phys. Condens. Matter. 19 (2007) 246208. tuational effects, J. Magn. Magn. Mater. 202 (1999) 535546. 47
5 [18] Y.A. Koksharov, S.P. Gubin, I.D. Kosobudsky, M. Beltran, Y. Khodorkovsky, A. [36] F. Bdker, S. Mrup, S. Linderoth, Surface effects in metallic iron nanoparticles, 48
M. Tishin, Low temperature electron paramagnetic resonance anomalies in Fe- Phys. Rev. Lett. 72 (1994) 282.
6 based nanoparticles, J. Appl. Phys. 88 (2000) 1587. [37] B.D. Cullity, Introduction to Magnetic Materials, IEEE/Wiley, Hoboken, N.J.,
7 1.373879. 2009. 50
8 [19] R.V. Upadhyay, K. Parekh, R.V. Mehta, Spin-glass-like magnetic ordering in Zn [38] B. Martinez, Low temperature Surface spin glass transition in -Fe2O3, Phys. 51
substituted magnetite magnetic uids, J. Magn. Reson. 187 (2007) 314319. Rev. B 80 (1998) 181183.
9 [20] R.V. Upadhyay, K. Parekh, R.V. Mehta, Spin-glass transition in a model [39] K. Parekh, R.V. Upadhyay, Magnetization dynamics in rare earth Gd 3
10 magnetic uid: Electron spin resonance investigation of Mn0.5Zn0.5Fe2O4 Mn0.5Zn0.5Fe2O4 magnetic uid: electron spin resonance study, J. Magn. Reson. 53
11 nanoparticles dispersed in kerosene, Phys. Rev. B. 68 (2003) 224434. 225 (2012) 4651. 54
[21] P.C. Morais, M.C.L. Lara, K.S. Neto, Electron spin resonance in superparamag- [40] C.R. Alves, R. Aquino, J. Depeyrot, T.A.P. Cotta, M.H. Sousa, F.A. Tourinho, et al.,
12 55
netic particles dispersed in a non-magnetic matrix, Philos. Mag. Lett 55 (1987) Surface spin freezing of ferrite nanoparticles evidenced by magnetization
13 181183. measurements, J. Appl. Phys. 99 (2006) 08M905. 56
14 [22] A.F. Bakuzis, P.C. Morais, F.A. Tourinho, Investigation of the magnetic aniso- 1.2163844. 57
15 tropy in manganese ferrite nanoparticles using magnetic resonance, J. Magn. [41] F. Gazeau , Thesis, Universite Pierre et Marie Curie,1997. Q8 58
Reson. A 122 (1996) 100103. [42] A.L. Tronconi, P.C. Morais, F. Pelegrini, F.A. Tourinho, Electron paramagnetic
16 [23] A.F. Bakuzis, P.C. Morais, F. Pelegrini, Surface and exchange anisotropy elds in resonance study of ionic water-based manganese ferrite ferrouids, J. Magn. 59
17 MnFe2O4 nanoparticles: size and temperature effects, J. Appl. Phys. 85 (1999) Magn. Mater. 122 (1993) 9092. 60
18 7480. [43] P.C. Morais, M.C.F.L. Lara, A.L. Tronconi, F.A. Tourinho, A.R. Pereira, F. Pelegrini, 61
[24] Y.L. Raikher, M.I. Shliomis, The effective eld method in the orientational Magnetic particleparticle interaction in frozen magnetic uids, J. Appl. Phys.
19 kinetics of magnetic uids, Adv. Chem. Phys. 87 (1994) 595751. 79 (1996) 7931. 62
20 [25] F. Gazeau, J.C. Bacri, F. Gendron, R. Perzynski, Y.L. Raikher, V.I. Stepanov, et al., [44] G.J. da Silva, P.C. de Morais, F.A. Tourinho, Electron paramagnetic resonance of 63
21 Magnetic resonance of ferrite nanoparticles: evidence of surface effects, J. doped magnetic uids: a new approach to probe the particle size polydis- 64
Magn. Magn. Mater. 186 (1998) 175187. persity, J. Phys. Chem. 100 (1996) 1426914271.
22 [26] V.P. Shilov, Y.L. Raikher, J.-C. Bacri, F. Gazeau, R. Perzynski, Effect of unidirec- [45] R.P. Morais, G.R.R. Goncalves, K. Skeff Neto, F. Pelegrini, N. Buske, Study of
23 tional anisotropy on the ferromagnetic resonance in ferrite nanoparticles, particleparticle interaction in magnetic uids using magnetic resonance, 66
24 Phys. Rev. B 60 (1999) 11902. IEEE Trans. Magn. 38 (2002) 32253227. 67
[27] V.P. Shilov, J.-C. Bacri, F. Gazeau, F. Gendron, R. Perzynski, Y.L. Raikher, TMAG.2002.802499.
25 Ferromagnetic resonance in ferrite nanoparticles with uniaxial surface aniso- [46] L.B. Silveira, J.G. Santos, F. Pelegrini, C. Gansau, N. Buske, P.C. Morais, Magnetic
26 tropy, J. Appl. Phys. 85 (1999) 6642. resonance study of zero-eld-frozen magnetite-based biocompatible mag- 69
27 [28] N.A. Frey, S. Peng, K. Cheng, S. Sun, Magnetic nanoparticles: synthesis, netic uid, IEEE Trans. Magn. 39 (2003) 26422644. 70
functionalization, and applications in bioimaging and magnetic energy sto- TMAG.2003.815539.
28 71
rage, Chem. Soc. Rev. 38 (2009) 25322542. [47] K. Parekh, R.V. Upadhyay, R.V. Mehta, D. Srinivas, Electron spin resonance
29 [29] M. George, A. Mary John, S.S. Nair, P.A. Joy, M.R. Anantharaman, Finite size study of a temperature sensitive magnetic uid, J. Appl. Phys. 88 (2000) 2799. 72
30 effects on the structural and magnetic properties of solgel synthesized 73
31 NiFe2O4 powders, J. Magn. Magn. Mater. 302 (2006) 190195. http://dx.doi. [48] K.H. Hsu, J.H. Wu, Y.Y. Huang, L.Y. Wang, H.Y. Lee, J.G. Lin, Critical size effects 74
org/10.1016/j.jmmm.2005.08.029. on the magnetic resonance in Fe3O4 nanoparticles, J. Appl. Phys. (2005) Q9
32 [30] R.C. Woodward, J. Heeris, T.G. Pierre St, M. Saunders, E.P. Gilbert, 114322-1114322-4 75
33 M. Rutnakornpituk, et al., A comparison of methods for the measurement of [49] K. Nadeem, H. Krenn, T. Traussing, I. Letofsky-Papst, Distinguishing magnetic 76
34 the particle-size distribution of magnetic nanoparticles, Appl. Crystallogr. blocking and surface spin-glass freezing in nickel ferrite nanoparticles, J. Appl. 77
(2007). Phys. 109 (2011) 013912.
35 [31] K. Parekh, R.V. Upadhyay, R.V. Mehta, D. Srinivas, Electron spin resonance [50] A.F. Bakuzis, L.C. BranquinhoL. Luiz e CastroM.T. de Amaral e EloiR. Miotto, 78
36 study of a temperature sensitive magnetic uid, J. Appl. Phys. 88 (2000) 2799. Chain formation and aging process in biocompatible polydisperse ferrouids: 79
37 experimental investigation and Monte Carlo simulations, Adv. Colloid Inter- 80
[32] F. Pelegrini, A.R. Pereira, P.C. Morais, Ferromagnetic resonance line of ferrite face Sci. 191192 (2013) 121.
38 ferrouids at high microwave power, J. Magn. Magn. Mater. 289 (2005) 8486.
39 82
40 [33] J.M. Vargas, E. Lima, R.D. Zysler, J.G. Duque, E. De Biasi, M. Knobel, Effective 83
anisotropy eld variation of magnetite nanoparticles with size reduction, Eur.
41 84
Phys. J. BCondens. Matter Complex Syst. 64 (2008) 211218.
42 85

Please cite this article as: A. Shankar, et al., Journal of Magnetism and Magnetic Materials (2014),