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 Mater. Res. Express 4 (2017) 086102 https://doi.org/10.1088/2053-1591/aa8674

PAPER

Magnetic behavior of NiO nanoparticles determined by SQUID

magnetometry
RECEIVED
29 June 2017
RE VISED
9 August 2017
ACCEP TED FOR PUBLICATION
Farrakh Shahzad1,2, Kashif Nadeem1,3, Julia Weber1, Heinz Krenn1 and Peter Knoll1
1
16 August 2017 Institute of Physics, Karl-Franzens University, Graz, Austria
2
PUBLISHED
Department of Physics, COMSATS institute of information technology, Islamabad, Pakistan
3
29 August 2017 Department of Physics, International Islamic University, Islamabad, Pakistan
E-mail: farrakh@ymail.com

Keywords: antiferromagnetic nanoparticles, SQUID magnetometry, field-cooled/zero-field cooled measurements, hysteresis curves,
temperature dependent measurements

Abstract
NiO nanoparticles (4 nm–80 nm diameter) are investigated by SQUID magnetometry. Hysteresis
loops at various temperatures and susceptibility versus temperature measurements using field-
cooled/zero-field cooled protocols at various magnetic fields are performed. The measurements
give evidence for a strong increase of magnetic moments with decreasing size of NiO nanoparticles.
From the dependence of the magnetic moment on temperature and external field, blocked
superparamagnetism is observed superimposed to the core antiferromagnetism of NiO-particles. A
quantitative estimate demonstrates that uncompensated surface spins contribute to a ferromagnetic-
like hysteresis modelled by a broad distribution of anisotropy fields at the surface induced by the
antiferromagnetic core.

Introduction

Scientific studies on nanoparticles have gained interest due to their complex properties. Being small the
nanoparticles show very different properties as compared to their bulk counterpart. Surface to volume ratio
increases as the reciprocal of the particle size and for ultra-small nanoparticles this ratio becomes very high. For
this case, many atoms reside on the surface which makes the behavior very complicated. Day by day new research
investigations are being published in the field of nanoparticles but still there is a mystery behind their unusual
behavior [1].
NiO is a transition metal oxide. It is antiferromagnetic in nature with a Néel temperature of 523 K. Below
523 K, it has a slightly distorted fcc unit cell which gains stability when squeezed inwards along the 1 1 1 direc-
tion. Thus, the unit cell undergoes a rhombohedral distortion. The structure of NiO changes to fcc (NaCl type)
above the Néel temperature and the magnetic phase is paramagnetic [2–8].
Various authors have reported distinct magnetic properties for antiferromagnetic nanoparticles. Tiwari and
Rajeev [2, 9] have studied NiO nanoparticles prepared by Sol-gel method. They investigated the magnetic sus-
ceptibility of small sized nanoparticles and proposed that these nanoparticles consist of antiferromagnetically
aligned spins in the core and frozen spins at the surface around this core. In their study, behavior of NiO nanopar-
ticles is not interpreted as blocked superparamagnetism, but rather spin-glass like due to freezing and disorder of
spins at the surface of particles. In another study [10] size dependent magnetic properties of NiO nanoparticles
have been investigated within a size range of 4–22 nm. Particles were prepared by sol–gel method. This study
also claims that NiO nanoparticles have core–shell structure, but spin glass behavior has not been considered.
The antiferromagnetic alignment of the core becomes progressively suppressed by the decrease of the particle
size. Ghosh et al performed zero-fielded-cooled/field-cooled (ZFC/FC) temperature scans and hysteresis meas-
urements on NiO nanoparticles prepared by a chemical method [11]. They reported that NiO nanoparticles
are superparamagnetic in nature. Various other authors have also reported superparamagnetic type of behavior
[12–19]. Anomalous magnetic behavior of NiO nanoparticles is observed in different studies [20, 21]. Various
authors have reported an exchange bias effect in NiO nanoparticles [22–26]. If the core–shell model is consid-
ered for NiO nanoparticles, an exchange bias phenomenon could be induced by exchange coupling between the

© 2017 IOP Publishing Ltd

Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 1.  FC/ZFC magnetization measurements for NiO nanoparticles at 50 Oe.

Figure 2.  FC/ZFC magnetization measurements for bulk-like particle sample (80 nm) and NiO single crystal at 50 Oe.

antiferromagnetic core spins and the partly unidirectionally oriented spins in the shell [27, 28]. Surface effects
play an important role with decreasing particle size. These effects are even more pronounced for antiferromagn­
etic nanoparticles because of the dominance of misaligned surface spins with a resulting net magnetic moment
of considerable size [29]. These surface induced anisotropy effects are studied by Zyslar et al for NiO nanoparti-
cles [30, 31]. Memory and aging effects are also reported for NiO nanoparticles with average sizes of 5 nm by tak-
ing FC and ZFC measurements. These effects are attributed to a spin glass behavior of NiO nanoparticles due to
freezing of spins at the surface of individual particles [32]. Interparticle interactions are believed to be of minor
importance for antiferromagnetic particles. However residual magnetic moments of misaligned surface spins
can also contribute to a magnetic coupling between such nanoparticles [33]. Seehra et al studied these effects for
NiO nanoparticles [34, 35]. They produced coated and uncoated NiO nanoparticles with and without oleic acid
cladding, observing a sizeable dipolar coupling between uncoated NiO-particles.
The cited literature signifies that NiO nanoparticles show very interesting magnetic properties on the nano-
scale which is still not very well understood. In this work NiO nanoparticles are prepared by Sol-gel technique,
details of which are presented in [36]. Magnetic measurements using a SQUID magnetometer should elucidate
the complex magnetism of small-sized NiO particles in dependence of their size and under specific magnetic
field and temperature scan protocols.

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 3.  FC/ZFC magnetization measurements for the 80 nm-sample at 500 Oe.

Figure 4.  Hysteresis curves for NiO nanoparticles at different temperatures for samples 45 nm and 80 nm.

All magnetic measurements mentioned in this research article are taken by a Quantum Design SQUID mag-
netometer MPMS-7-XL, the facility available at Institute of Physics, Karl-Franzens University, Graz, Austria. For
this purpose, powdered sample is filled into a capsule and put in sample holder. The magnetic behavior of capsule
material is subtracted from all measurements to get actual behavior of NiO samples.

Field cooled/zero field cooled susceptibility measurements for NiO nanoparticles

Field cooled and zero field ‘FC/ZFC’ cooled measurements are taken for NiO nanoparticles of different sizes
and compared with large bulk-like particles which mimic a NiO single crystal. According to the ZFC-protocol,
the sample is cooled first to 4.2 K in zero magnetic field, then an external magnetic field of 50 Oe is switched
on and the magnetization is measured with the increasing temperature. The measurement is taken up to room
temperature (300 K). At this stage, the external field is kept constant, and the ‘FC’-curve is measured by reversing
the temperature from 300 K down to 4.2 K. FC/ZFC measurements for NiO nanoparticles of various diameters
and for bulk NiO (compared with 80 nm particles to mimic ‘single’ crystal) are shown in figure 1. The scale of

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 5.  Zoomed hysteresis curve to display coercivity for NiO-sample 45 nm for various temperatures.

Figure 6.  Zoomed hysteresis curve to display coercivity for NiO-sample 80 nm at T  =  4.2 K and T  =  300 K.

magnetization-curves of single crystal and NiO-particles 80 nm (‘single’ crystal like) is magnified in figure 2 to
compare their hysteretic splitting between FC/ZFC curves. FC/ZFC measurement is also taken at higher external
field of 500 Oe for the 80 nm diameter sample. This measurement is shown in figure 3.
A common feature of frozen spin systems (spin-glasses) is an extended splitting of ZFC/FC-curves over a
wide temperature range from lowest (4.2 K) to highest temperatures (350 K), particularly observed for the small-
est particles, see figure 1.
An enhanced splitting between ZFC and FC-curves (figure 2) is also observed for the largest 80 nm particles
in comparison to the bulk crystalline sample. The normalized magnetization of 80 nm (magnetic moment per
mass unit) is considerably higher than for the single NiO-crystal sample due to uncompensated spins at the sur-
face. As it is known from spin-glasses, ZFC/FC-splitting is reduced if the magnetic field is increased (as observed
in figures 2 and 3 for 50 Oe and 500 Oe, respectively).

Hysteresis measurements for NiO nanoparticles

Hysteresis curves are measured for NiO nanoparticles of varying diameter at different temperatures (4.2–400 K).
Figure 4 shows as an example the hysteresis loop for samples with average size of 45 nm and 80 nm at various

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 7.  Hysteresis curves for NiO nanoparticles at different temperatures for sample 4 nm at different temperatures.

Figure 8.  Zoomed hysteresis curve to display coercivity for NiO-sample 4 nm at different temperatures.

temperatures noted in the figure. Selected area in the rectangular frame of figure 4 is zoomed in the following
figure 5. An open hysteresis loop (with finite coercivity) is observed for the 45 nm sample while residual coercivity
is also present for the 80 nm NiO nanoparticles in figure 6. Hysteresis curves for smaller size (4 nm) nanoparticles
are shown in figure 7 and zoomed area is shown in figure 8 to show corresponding coercivity for various
temperatures.
The temperature dependence of coercivity is plotted in figure 9 for various samples. It is observed that coer-
civity decreases for increasing particle diameter, whereas it increases for decreasing temperature for a chosen
specific sample. As it is also shown in figure 9, all hysteresis curves collapse to a unique curve (of zero coercivity)
for temperatures above 500 K near the Néel temperature.

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 9.  T-dependent coercivity of NiO-nanoparticles of different diameters.

Figure 10.  Hysteresis curve of a typical blocked superparamagnetic material (solid curve) for magnetic field along the anisotropy
axis, and non-hysteretic reversible magnetization (dashed curve) for magnetic field perpendicular to the easy axis. Ms is the
saturation magnetization, Mr the remanent field and Hc the coercive field.

A typical rectangular-shaped hysteresis curve of blocked superparamagnetic particles is shown in figure 10.

Such a hysteresis loop is observed for a unique anisotropy axis along the magnetic field. Switching between satur­
ated states (±Ms) takes place at coercive forces  ±Hc which is rather high in blocked particles. Such behavior of
blocked single domain particles is described by the Stoner–Wohlfarth model. For a random anisotropy ‘easy‘
axis direction an admixture of hysteretic and non-hysteretic branches are superimposed (see both extreme cases
in figure 10) with a corresponding smoothing of the rectangular hysteresis loop. In contrast, unblocked super-
paramagnetic particles (at elevated temperature) of very small size can relax and fluctuate due to thermal agita-
tion and hysteretic behavior is lost, see references [37–39].
Blocked and relaxed superparamagnetism is also expected in particles consisting of antiferromagnetically
compensated core and of uncompensated shell spins. Contrary to ferromagnetic particles the number of ‘fer-

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 11.  Example of a linear fit to the non-saturation of the hysteresis curve for sample 45 nm.

Figure 12.  Antiferromagnetic susceptibility for NiO nanoparticles of various sizes. Blue curve represents data simulated by the
Heisenberg model in bulk NiO of random crystal orientation.

romagnetic’ surface spins of antiferromagnetic NiO-particles is much less. These spins are exposed to a strong
unidirectional anisotropy by exchange bias with the antiferromagnetic core. The interplay between surface and
core magnetism for NiO nanoparticles is reflected in the appearance of a ‘ferromagnetic-lik’ hysteresis of finite
coercivity, but with a missing saturation behavior, since the antiferromagnetic exchange interaction between the
core spins cannot be completely released in magnetic fields up to a few tens of Tesla.
According to Kelso et al [40, 41] it is possible to separate the effect of core and shell spins. The saturation
branches of the hysteresis curve are fitted linearly by the straight (red) lines in figure 11. The saturation mag-
netization Ms is obtained after subtraction of this linear slope-curves, and the remainder represents the super-
paramagnetic susceptibility χ, which is fitted to a steep turn-up of the magnetization curves for small magnetic
fields.
Measured and calculated susceptibility are plotted in figure 12. For powdered NiO samples the susceptibility
curve (blue line) is calculated from a Heisenberg model and compared with the measured data.

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 13.  T-dependent saturation magnetization (@ H  =  7 T) for NiO nanoparticles of various sizes.

Figure 14.  Two points marked by red lines on the linear part of hysteresis curves.

Magnetization versus temperature measurements for NiO nanoparticles

Antiferromagnetic particles exhibit an altered temperature dependency below the Néel temperature compared
with superparamagnetic particles. Measured and calculated susceptibility is plotted in figure 12. For bulk and
powdered NiO samples of random crystal orientation the susceptibility curve (blue line) is calculated from a
Heisenberg model and compared with the measured data.
The temperature dependent saturation magnetization determined after subtraction of the linear slope
(exemplified by figure 11) is shown in figure 13.
It can be seen from the plot of susceptibility and saturation magnetization in figures 12 and 13 that these
data are taken for external values (7 T) of magnetic field in the saturation range. To get additional data for the
temperature dependence, two more adjacent magnetic fields (3 T and 0.3 T, see figure 14) were selected at which

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 15.  Magnetization versus temperature measurements for particles of d  =  45 nm at 0.3 T and 3 T

Figure 16.  Temperature-dependent susceptibility for NiO nanoparticles of d  =  80 nm, 45 nm, 4 nm.

temperature versus magnetization measurements are collected. The results of these measurements are shown
(e.g. sample 45 nm) in figure 15.
Susceptibility values between these two fields (after division by the magnetic field) are averaged and then val-
ues for susceptibility and saturation magnetization are drawn as solid lines in figures 16 and 17. For comparison,
the results taken from the hysteresis loops are also shown.

Contributions of the surface magnetization in NiO nanoparticles

Bulk materials have negligible surface contributions. But for nanoparticles the surface contribution becomes
important. The surface contribution increases with the decrease of the particle size as more atoms reside on the
surface. So, it is important to get knowledge of the surface and bulk contributions to the magnetization with
decreasing particle size [1].

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 17.  Saturation magnetization (@ H  =  7 T) for NiO nanoparticles samples 45 nm, 80 nm, 4 nm.

Figure 18.  Bulk and surface magnetizations calculated for spherical NiO nanoparticles.

Surface magnetization (in emu g−1) is calculated for different sizes of NiO nanoparticles. Cubic shape nano-
particles are considered for this purpose. Surface magnetization can be calculated by the following formula:

M = µ Ni
NNi S
A ( )( )
V
1
ρ .

Where ρ  =  6.67 g cm−3 is the mass density of NiO, µ Ni = gµ BS = 2µ B is the atomic magnetic moment for a single
Ni atom (S  =  1), µ B is the Bohr magneton, g-factor is taken as 2, S/V is the surface to volume ratio, for a cube of
6a2 6
edge-length a: S/V  =   a3 = a , and NNi the number of Ni atoms in the cube, A is the total surface area of the
cube (6a2). For calculating NNi we have taken differently structured cubes facetted by (1 1 1)- and (1 0 0)-surfaces,
respectively.
The results are presented in figure 18. It is assumed that all surface Ni-spins are ferromagnetically aligned
which results in a total magnetization of around 150 emu g−i. The calculations revealed that surface magnetiza-

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 19.  Comparison of the calculated surface magnetization (dashed curves) with measured data (square dots).

tion increases while bulk magnetization decreases with the decrease of the particles size. This variation in mag-
netization becomes drastic for particles sizes below 10 nm.
The surface magnetization (taken from figure 18) and saturation magnetization (taken from figures 12 and 17)
are compared to each other, see figure 19. It is observed that the measured saturation magnetization is close to the
calculated surface magnetization, the over-estimation of calculated values originates from the previous assump-
tion, that all spins on the surface are ferromagnetically aligned, which is generally not the case.

Discussion

Magnetization measurements on NiO nanoparticles have been presented in dependence of the magnetic field
and temperature. FC/ZFC scans for NiO nanoparticles have shown that the magnetic moment increases with the
decrease of particle size, a phenomenon which has been predicted already by Néel [42]. The splitting between FC
and ZFC curves also increases as the particle size is reduced and becomes negligible for a NiO single crystal and for
large-size nanoparticles of 80 nm. However, such splitting appears for NiO nanoparticles near and below 45 nm
and it progressively increases for sizes down to the smallest particles of 4 nm. Enhanced splitting and increase of
magnetic moment with decreasing particle size are attributed to finite size effects [43]. The FC/ZFC curve for
the 80 nm-sample measured at higher external field of 500 Oe has shown a smaller splitting and an enhanced
magnetic moment. This means that higher magnetic field has facilitated more surface spins to get aligned with
the magnetic field. Past research studies have reported on the superparamagnetic behavior of very small NiO
nanoparticles [12–18]. They document the appearance of blocking behavior with a peak in the ZFC curve. Our
FC/ZFC measurements on NiO nanoparticles of sizes  >4 nm have not shown any hint of magnetic blocking in
the temperature range (4.2–300 K). It is believed that the missing blocking peak (even for temperatures above
room temperature) and the non-vanishing splitting in FC/ZFC up to 300 K is either a fingerprint for freezing
of surface spins or such a behavior is reflected by a broad magnetocrystalline surface anisotropy distribution
function (up to 1 MJ m−3) of blocked superparamagnetic particles with a predominant orientation along the
antiferromagnetic orientation of the core.
The coercivity (figure 9) shows a strong temperature dependency and increases with decreasing particles size,
vanishing for single crystals and large-size nanoparticles (90 nm). It is highest for nanoparticles of 4 nm. By inves-
tigating the field-dependent magnetization well above 500 K, there is still a rather strong cooperative interaction
between the surface spins [37, 38].
Figure 20 shows the hysteresis loops for ultra-small (4 nm) NiO particles for temperatures in the ferromagn­
etically aligned surface regime (T  =  4.2 and 25 K).
The increase of coercivity with decreasing particle size and the open area hysteresis loops even for high fields
indicate a broadening of the anisotropy field acting on the surface spins. In the same way, the saturation mag-
netization increases with decreasing particle size (figure 13) and indicates an increase of the number of ferro-
magnetically coupled spins. Compared with the estimated maximum possible (surface and core) spins of the
nanoparticles, the mere contribution of surface spins is responsible for this behavior.

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Mater. Res. Express 4 (2017) 086102 F Shahzad et al

Figure 20.  Constricted and open hysteresis loops for ultrasmall (4 nm) NiO nanoparticles for T  =  4.2 and T  =  25 K. A broadened
T-dependent anisotropy energy distribution up to 1 MJ m−3 has been adopted for the model fit instead of surface freezing.

Susceptibility curves of figures 12 and 16 can be compared with calculations according to the Heisenberg
model for a powder NiO sample. It is observed that large size nanoparticles of 80–90 nm obey antiferromagnetic
behavior. Particles of 45 nm size behave antiferromagnetic at higher temperature, but convert to superparamagn­
etic behavior with the decrease of temperature. This can be observed by the upturn of the susceptibility curves
at lower temperatures (figure 16). Nanoparticles of small size (4 nm) show a quite different behavior, exhibiting
increased magnetic moment and a constricted and open hysteresis loop up to high magnetic fields. Figure 20
shows an example and compares measured data with a model fit with regard of a broadened anisotropy distribu-
tion function acting on the surface spins.

Conclusion and summary

Summarizing the results, an interesting surface-core cooperative magnetic behavior of small

antiferromagnetic NiO particles has been demonstrated. Néel’s prediction of a broad magnetocrystalline
surface anisotropy distribution is proved by the increase of a non-zero saturation magnetization with
decreasing particle size and predominant surface anisotropy. A more thorough analysis of the constricted
and open hysteresis loops for ultrasmall particles at elevated magnetic fields demonstrates a temperature-
variable magnetic anisotropy energy distribution with a progressive broadening in the surface regime
of individual particles toward low temperatures and small diameter. Interparticle interaction due to
dipolar coupling is neglected for nominally antiferromagnetic particles, thus a ‘super-spin-glass’ can be
excluded.

References
[1] Fiorani D 2005 Surface Effects in Magnetic Nanoparticles (Rome: Springer)
[2] Tiwari S D and Rajeev K P 2006 Magnetic properties of NiO nanoparticles Thin Solid Films 505 113–7
[3] Rooksby H P 1948 A note of structure on nickel oxide at subnormal and elevated temperatures Acta Cryst. 1 226

12
Mater. Res. Express 4 (2017) 086102 F Shahzad et al

[4] Tombs N C and Rooksby H P 1950 Structure of Monoxides of some transition elements at low Temperatures Nature 165 442–3
[5] Greenwald S and Samuel Smart J 1950 Deformations in the crystal structures of Anti-ferromagnetic compounds Nature 4221 523–4
[6] Slack G A 1960 Crystallography and domain walls in antiferromagnetic NiO crystals J. Appl. Phys. 31 1571–82
[7] Robell D S and Owen J 1964 Sublattice magnetization and lattice distortion in MnO and NiO J. Appl. Phys. 35 1002–3
[8] Samuel Smart J and Greenwald S 1951 Crystal structure transitions in antiferromagnetic Phys. Rev. 82 113–4
[9] Tiwari S D and Rajeev K P 2005 Signatures of spin-glass freezing in NiO nanoparticles Phys. Rev. B 72 10443
[10] Thota S and Kumar J 2007 Sol-gel synthesis and anamolous magnetic behavior of NiO nanoaparticles J. Phys. Chem. Solids 68 1951–64
[11] Moumita G et al 2006 MnO and NiO nanoparticles: synthesis and magnetic properties J. Mater. Chem. 16 106–11
[12] Davara F, Fereshteh Z and Salavati-Niasari M 2009 Nanoparticles Ni and NiO: synthesis, characterization and magnetic properties
J. Alloys Compd. 276 797–801
[13] Abdul Khadar M et al 2003 Effect of finite size on the magnetization behavior of nanostructured nickel oxide Mater. Res.
Bull. 38 1341–9
[14] Ichiyanagi Y et al 2003 Magnetic properties of NiO nanoparticles Physica B 329–33 862–3
[15] Seto T et al 2005 Magnetic properties of monodispersed Ni/NiO core–shell nanoparticles J. Phys. Chem. B 109 13403–5
[16] Narsinga Rao G, Yao Y D and Chen J W 2005 Superparamagnetic behavior of antiferromagnetic Cuo nanoparticles IEEE Trans. Magn.
41 3409–11
[17] Yi J J B et al 2008 The structure and magnetic properties of NiO with different sizes 2008 2nd IEEE Int. Nanoelectronics Conf. (ICNEC
2008) pp 1047–50
[18] Richardson J et al 1991 Origin of superparamagnetism in nickel oxide J. Appl. Phys. 70 6977–82
[19] Suresh R et al 2017 NiO nanoflakes: effect of anions on the structural, optical, morphological and magnetic properties J. Magn. Magn.
Mater. 441 787–94
[20] Makhlouf S A et al 1997 Magnetic anomolies in NiO nanoparticles J. Appl. Phys. 8 5561–3
[21] Li L et al 2006 Magnetic crossover of NiO nanocrystals at room temperature Appl. Phys. Lett. 89 134102
[22] Lindgard P-A 2009 Switching behavior of coupled antiferro- and ferromagnetic systems: exchange bias J. Phys.: Condens. Matter
21 474225
[23] Sharma S K et al 2010 The nature and enhancement of magnetic surface contribution in model NiO nanoaparticles Nanotechnology
21 035602
[24] Jagodic M et al 2009 Surface-spin magnetism of antiferromagnetic NiO in nanoparticle and bulk morphology J. Phys.: Condens. Matter
21 215302
[25] Rinaldi-Montes N, Gorria P, Martinez-Blanco D and Fuertes A B 2016 Bridging exchange bias effect in NiO and Ni(core)@NiO(shell)
nanoparticles J. Magn. Magn. Mater. 400 236–41
[26] Gandhi A C and Lin J G 2017 Exchange bias in finite sized NiO nanoparticles with Ni clusters J. Magn. Magn. Mater. 424 221–5
[27] Silva F G et al 2010 Exchange bias properties and surface spin freezing in ferrite nanoparticles of magnetic nanocolloids Int. Conf. on
Magnetism (ICM 2009) vol 200 p 072035
[28] Meiklejohn W H and Bean C P 1956 New magnetic anisotropy Phys. Rev. 102 1413–4
[29] Trohidou K N, Ziann X and Blackman J A 1998 Surface effects on the magnetic behavior of antiferromagnetic particles J. Appl. Phys.
84 2795
[30] Winkler E et al 2005 Surface anisotropy effects in NiO nanoparticles Phys. Rev. B 72 132409
[31] Zyslar R D et al 2006 Surface effects in the magnetic order of antiferromagnetic nanoparticles Physics B 384 277–81
[32] Bisht V and Rajeev K P 2010 Memory and aging effects in NiO nanoparticles J. Phys.: Condens. Matter 22 016003
[33] Bodker F et al 2000 Particle interaction effects in antiferromagnetic NiO nanoparticles J. Magn. Magn. Mater. 221 32–6
[34] Seehra M S et al 2005 Interparticle interaction effects in the magnetic properties of NiO nanorods J. Appl. Phys. 97 10J509
[35] Seehra M S et al 2006 Effect of interparticle interaction on the magnetic relaxation in NiO nanorods J. Appl. Phys. 99 08Q503
[36] Shahzad F, Ettinger K, Letofsky-Papst I, Weber J and Knoll P 2015 Preparation and characterization of NiO nanoparticles J. Nano Res.
31 93–102
[37] Blundell S 2001 Magnetism in Condensed Matter (Oxford Master Series in Condensed Matter Physics) (Oxford: Oxford University Press)
[38] Guimaras A P and Oliveira I S 1998 Magnetism and Magnetic Resonance in Solids (New York: Wiley)
[39] Tarling D H and Hrouda F 1993 Magnetic Anisotropy of Rocks (London: Chapman and Hall)
[40] Kelso P R, Tikoff B and Jackson M 2002 A new method for the separation of paramagnetic and ferromagnetic susceptibility anisotropy
using low field and high field methods Geophys. J. Int. 151 345–59
[41] Martin-Hernandez F and Hurt A M 2004 A new method for the sepration of paramagnetic, ferrimagnetic and haematite magnetic
subfabrics using high-file torque magnetometry Geophys. J. Int. 157 117–27
[42] Néel L 1961 Superantiferromagnetisme dans les grains fins C. Rendus Hebd. Séances Acad. Sci. 253 203–6 [http://gallica.bnf.fr/
ark:/12148/bpt6k3205m/f213.image.r=Superantiferromagnetisme%20dans%20les%20grains%20fins?rk=64378;0]
[43] Zheng X G et al 2005 Finite size effects on Neel temperature in antiferromagnetic nanoparticles Phys. Rev. B 72 014464

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