Magnetic structure of small NiFe2O4 particles

A. H. Morr and K. Haneda

Citation: J. Appl. Phys. 52, 2496 (1981); doi: 10.1063/1.328979
View online: http://dx.doi.org/10.1063/1.328979
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Published by the American Institute of Physics.

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Magnetic structure of small NiFe
2
0
4
particles
A. H. Morrish and K. Haneda*
Department of Physics, University of Manitoba, Winnipeg, Manitoba, Canada R3T 2N2
The magnetic structure of small NiFe,O. particles has been investigated. Samples (in the few hundred
angstrom size range and up) were prepared by chemical precipitation followed by a heat treatment at
relatively low temperatures. Mossbauer spectra of the 57Fe nuclei, obtained with a longitudinal magnetic field
applied, unambiguously establish that a noncollinear structure exists. Further, the magnetic moment at low
temperatures is appreciably lower than the value reported for bulk materiaL A model is proposed in which the
NiFe,O. particles consist of a core with the usual spin arrangement and a surface layer with atomic moments
inclined to the direction of the net magnetization. The temperature dependence of this structure is also
reported.
PACS numbers: 68.20. + t, 75.25. + z, 75.50.Gg, 75.60.Jp
INTRODUCTION
Nickel ferrite (NiFe204) is an inverse spinel in
which the tetrahedral or A-sites are occupied by ferric
ions, and the octahedral or B-sites by ferric and nick-
el ions. Thus, the can be represented by the
formula where the round and
square brackets represent A and B sites, respectively.
The magnetic structure is generally assumed to be the
Neel collinear type, that is, the magnetization of the
A sublattice is antiparallel to that of the B sublat-
tice (1). Definitive evidence for this model has been
provided by Chappert and Frankel (2) from Mossbauer
measurements taken with the application of large mag-
netic fields. A dissenting report, apparently the only
one, was made by Kedem and Rothem (3) on the basis of
the line widths in their Mossbauer spectrum; they pro-
pose that NiFe204 has a Yafet-Kittel type of spin ar-
rangement (4) with four hyper fine field patterns.' It
may be noted that Morel (5) has suggested that a strong
positive exchange interaction acts between the Ni
2
+ and
the Fe
3
+ ions on the B sites; such an interaction would
tend to inhibit a Yafet-Kittel spin arrangement.
In almost all the investigations reported to date,
the nickel ferrite has been in the form of micron or
almost-micron sized particles. However, a few inves-
tigations on ultrafine NiFe204 particles are to be
found in the literature (6-10).
Recently, Mossbauer studies of small Y-Fe203 par-
ticles, which have usually been assumed to have a col-
magnetic structure consisting of two sublattices,
have revealed that a non-collinear spin arrangement
exists, primarily at or near the surface (11). Fur-
ther, this spin canting gradually decreases with in-
creasing temperature. In order to determine if this
effect occurs more generally, the magnetic structure
of small NiFe204 particles has been investigated by
57Fe Mossbauer spectroscopy and is the subject of this
report.
EXPERIMENTAL
Small particles of NiFe204 (in the few hundred
angstrom size range and up) were prepared by chemical
precipitation and subsequent heat-treatment at relati-
vely low temperatures for extended periods of time.
Three samples, each with different particles sizes, and
labelled A, B, and C, were made by changing the ther-
mal conditions during the heat-treatment for the dried
precipitates. Electron-microscope photographs, x-ray
fluorescence measurements, room temperature x-ray dif-
fraction patterns, magnetization data at 4.2 and 77 K,
and Mossbauer spectra at 77 and 300 K were then ob-
tained. In addition, Mossbauer spectra were taken with
a large magnetic field applied along the propagation
direction of the y-rays for the temperature range from
4.2 to 280 K. The data were analyzed with a least-
squares computer program that assumed the line shapes
were Lorentzian.
RESULTS AND DISCUSSION
A typical example of the electron-microscope pho-
tographs is shown in Fig. 1 for sample A. A distribu-
tion in size exists that for some unknown reason was
more pronounced for sample B. The median size for each
sample is listed in Table I. Information on the crys-
tallite size was deduced from x-ray line broadening
using the Sherrer formula, and is also given in Table I.
The chemical composition, as determined by x-ray fluo-
rescence, was close to the nominal values, within the
experimental errors. However, the data did indicate
that for samples A and B the composition may have been
closer to NiO.9Fe2.104.
Fig. 1. Electron photomicrograph of small NiFe204
particles in sample A.
TABLE I: Data for NiFe204 samples A, B, and C.
Sample Particle size Crystallite size
(R) (1\)
A 250 50 250
B 800 200 400
C 1300 200 500
2496 J. Appl. Phys. 52 (3), March 1981 0021-8979/81/032496-03$1.10 1981 American Institute of Physics 2496
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Mossbauer spectra obtained at 300 K are shown in
Fig. 2. These spectra are easily interpreted as two
six-line hyperfine patterns corresponding
to the 'Fe in B- and A-sites. Comparison of these
spectra provides some idea of the difference in the
particle sizes. In contrast to the fairly sharp line
profile for sample C. the spectrum for sample A exhi-
bits line-broadening and a slightly reduced hyperfine-
field splitting. This trend. although less pronounced.
is present in the 77 K data as well. The small reduc-
tion in hyper fine field for sample A may be related to
the collective excitation mechanism proposed by
and Topse (12.13). In brief. below the superparamag-
netic blocking temperature. thermally excited oscilla-
tions of the magnetization around an energy minimum re-
duce the magnetic hyperfine splitting in the Mossbauer
spectrum. and lead to broadened lines.
as observed.
In order to examine the spin arrangement. Moss-
bauer spectra were taken with a large longitudinal mag-
netic field applied. In a collinear magnetic system.
the atomic moments lie along the direction of the ex-
ternal magnetic field. and the polarization conditions
require the disappearance of the 6m = 0 lines in the
hyperfine pattern. Mossbauer spectra in magnetic
fields of 70 or 66.5 kOe applied parallel to the direc-
0.82
0.81
UJ

Z
=>
0
u
<l
(!)
ILl

1.28
1.26
1.24
1.22

VELOCITY (mm /s).
': i
A
8
Fig. 2. Mossbauer spectra of small NiFe204 particles
taken at 300 K. for (a) sample A. (b) sample B.
and (c) sample C.
tion of the Y-ray at T = 4.2. 100. and 280 K are shown
in Figs. 3 and 4 for the samples A and C. These spec-
tra were taken with a triangular-shaped drive and then
folded. Clearly. the Fe spins in NiFe204 are canted
from the direction of the external magnetic field since
substantial second and fifth absorption lines are ob-
viously present. The is most pronounced in
the smallest particles (sample A) and becomes less at
280 K of sample C (Fig. 4(b)]. where the statistics of
the spectrum were not ideal.
The data were analyzed with a least-squares compu-
ter program assuming 12 Lorentzians; same parameters
obtained are given in Table II. The ratio of the B to
A-site patterns for sample C at T = 4.2 K is very close
to the 1.00 expected for nickel ferrite. At room tem-
perature. the counting statistics. differences in the
recoilless fraction at the two sites, and perhaps other
factors may be the origin of the too large areal ratio
observed. For sample A, the B to A-site ratio is
O. 146 r..,....oon>-....
0.142
0.138
0.134
(c)
B
____ L-__ -L __ -L ____ __ A
VE LOCITY (mm /s )
Fig. 3. Mossbauer spectra taken in a longitudinal
external magnetic field of 70 kOe for small
NiFe204 particles, (a) at 4.2 K for sample A,
(b) at 100 K for sample A, and (c) at 4.2 K
for sample C.
.' .
TABLE II. Parameters deduced from Mossbauer spectra of small NiFe204 particles in a longitudinal magnetic
field.
Sample Temperature Applied field Area ratio
K (kOe) (B/A)
A 4.2 70.0 1.33
100 70.0 1.42
280 66.5 1.22
C 4.2 70.0 1.01
280 66.5 1.11
a
Insufficient statistics to calculate.
2497 J. Appl. Phys., Vol. 52, No.3, March 1981
Rhf (A)
(kOe)
571
565
559
583
570
(B)
Average canting angle (deg)
(kOe) , A-site B-site both sites
504 41 35 37
498 45 31 38
470 46 38 42
505 21 30 26
471 a
Magnetism & Magnetic Materials-1980 2497
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0.148, ,: .
en 0.145
....
z
g 0.142
u
c:t
0. eo -
0.368 ... :.' .
':""''' .... ,"::' ..... . ......
..:;. , ... ".0 "0 : .. :.:. 0-.
0.364
o ::
.'
0.360

VELOCITY (mm/s)
Ie #.: .
. ..... ".-;
(0 )
.. 0.
.," (b)
Fig. 4. Mossbauer spectra t4ken at 280 K in a longi-
tudinal external magnetic field of 66.5 kOe for
(a) sample A and (b) sample C.
clearly too large for a completely inverse nickel fer-
rite. However, from Fig. 3(a) it may be noted that the
outermost B lines are considerably broader than the
corresponding A lines. Further, the second and fifth
lines are broad and unresolved, and therefore may not
be properly separated into A and B-site components.
There is also the possibility that the Sample is not
completely inverse, or even not stOichiometric; no
firm conclusions in these directions is warrented at
this time.
The average spin canting angle, 0, between the
direction of propagation of the y ray and the direction
of the magnetization is given in Table II. It should
be noted that the canting angles for sample A appear
to be almost independent of the temperature over the
range from 4.2 to 300 K, in contrast to the earlier
results on y-Fe203 (11).
The hyper fine field at B sites decreases more ra-
pidly with increasing temperature than that at A sites.
This trend agrees generally with the observations of
Morel (5) and Sawatzky et al (11:). Further, the mag-
nitudes of the hyperfine field in the external magnetic
field as compared to the hyper fine field in zero ap-
plied field provide additional support for spin canting
on both A and B sublattices.
Magnetization measurements were conducted in a
magnetic field up to 16 kOe. The saturation magnetiza-
tion at 4.2 and 77 K was obtained by extrapolating to
l/H = O. The results are shown in Table III together
with previously reported bulk values. The saturation
magnetization of the small particles is significantly
lower, probably indicating some change in the magnetic
structure.
Now, in niCkel ferrite the net magnetization has
its origin essentially in the nickel magnetic moments.
Therefore, it fOllows that the nickel spin direction
must also be canted, almost to the same extent as the
iron spins on the B sites. The enhanced coercivity ob-
served in the small particles (Table III) indicates
that some sort of additional anisotropy has developed.
The magnetic of small NiFe204 particles
coated with organic surfactants was examined earlier by
Berkowitz et al (9,10). They reported that when the
particles were coated with an organic surfactant, a
strongly pinned non-collinear structure appears. On
removal of the organic coating by a heat-treatment, the
normal nickel ferrite spin structure was restored.
Their results seem to be somewhat at variance with the
present observations. However, their small particles
were obtained by grinding rather than by the chemical
methods used here. Further, it seems possible that
some secondary effects may be acting.
2498 J. Appl. Phys., Vol. 52, No.3, March 1981
TABLE III. Magnetic properties of small NiFe204
particles.
Sample Temperature as(emu/g)
iHc
(Oe)
(K)
A 77
32.6 600
4.2 31.5
B 77 37.6 500
4.2 38.9
C 77
40.9 220
4.2 41.1
Bulka
4.2
:;;
53
295
:;;
50
a
Reference 10.
Although normally it is not easy to distinguish
between size and surface effects in small particles, a
closer look at the spectra in Figs. 3'and 4 yields some
additional information. The theoretical interval bet-
ween the 1 and 6 lines, calculated from the interval
between the 2 and 5 lines, does not correspond to the
interval observed between the 1 and 6 lines. Since the
2-5 lines are solely the result of the non-collinear
structure, the 1-6 lines may be partially associated
with a bulk collinear structure. The observed pheno-
menon then may not be a size effect, but instead be re-
lated to a surface layer in which the spins are incli-
ned to the direction of the net magnetic moment. There-
fore, the NiFe204 particles may be visualized as having
a core with the normal spin arrangement and a surface
layer in which the spin arrangement takes a non-colli-
near structure. More definitive conclusions should be
possible if s7Fe were introduced preferentially into
the surface layers of the particles.
ACKNOWLEDGEMENTS
The authors are grateful to P. J. Picone of
the University of Manitoba for the magnetization mea-
surements and other helpful assistance in the experi-
ments. The research was supported financially by the
Natural Sciences and Engineering Research Council of
Canada.
*
1)
2)
3)
4)
5)
6)
REFERENCES
Present address: Research Institute for Scienti-
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Magnetism & Magnetic Materials-1980
2498
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