J. M. D. COEYand D.

KHALAFALLA:
Superparamagnetic y-Fe,O, 229

phys. stat. sol. (a) 11,229 (1972)

Subject classification: 5 and 18.1; 22.6

Department of Physics, University of Manitoba, Winnipeg

Superparamagnetic y-Fe,O,
BY
J. M. D. C O E Y ~and
) D. KHALAFALLA
Static magnetization and Mossbauer measurements on ultra-fine crystallites (.= 65 8)
of y-Fe,O, show them to be superparamagnetic a t 296 O K with an average relaxation time
of 2 x s. The particle size distribution is derived from the magnetization curve which
exhibits no hysteresis, and independently from the temperature variation of the ratio of
remanence to saturation magnetization. Mossbauer spectra a t 5 OK in an applied field of
up to 50 kOe show a cation distribution of 1 : (1.71 k0.05) for A and B sites, and a non-col-
linear spin arrangement. The low value of the magnetization, 59 e.m.u./g a t 4.2 “K for
1/H = 0, is explained by assuming that the spins of cations, which lie in the surface layer,
make random angles between 0 and 90” with the direction of the net moment. Allowance
is also made for water adsorbed onto the particle surface. When a field is applied to the
absorber a t 296 OK the spectrum changes from a broad single peak into two broadened
hyperfine patterns from A and B sites which are explained by the magnetic polarization
and range of ordering temperature of the particle distribution.
On a montre par des mesures d’aimantation statique et d‘effet Mossbauer que les grains
ultra-fins ( ~ 6 A)5 de y-Fe,O, sont superparamagnetiques & 296 O K avec un temps de relaxa-
tion moyen de 2 x 10-9 s. On a determine la fonction de distribution de la taille des grains
par la forme de la courbc d’aimantation (sans hysteresis) et, si:par&ment,par la variation
du rapport de l’aimantation remanente & I’aimantation & saturation en fonction de la temp&-
rature. Les spectres Mossbauer It 5 OK dans un champ appliqui: allant jusqu’h 50 kOe in-
diquent que les cations sont distribues sur les sites A et B dans le rapport 1 & 1,71 k 0,05,
et que la structure magnbtique des spins n’est pas collinbaire. On explique la faible valeur
de I’aimantation (59 u.e.m./g & 4,2 OK pour 1/H = 0) en supposant que les spins des cat-
ions de la couche superficielle font avec l’aimantation moyenne un angle compris entre 0
et 90”. On tient compte aussi de l’eau adsorbbe sur la surface des grains. A 296 “K,le spectre,
qui comprend une seule raie large, se transforme sous l’effet d’un champ applique en deux
spectres hyperfins Blargis provenant des sites A et B. On explique ce resultat par la polari-
sation magnbtique et la gamme des temperatures d‘ordre reliee & la fonction de distribution
des tailles des cristallites.
1. Introduction
Superparamagnetism occurs in particles of magnetically ordered material
which are so small t h a t the energy barrier t o changes in the direction of their
net moment is comparable t o thermal energies, and relaxation between the
various easy-directions is rapid compared t o the characteristic time of the
measurement. The superparamagnetic relaxation time, z, has been calculated
by Aharoni [l] for particles with uniaxial anisotropy, K and volume V , both
in the presence and absence of an applied magnetic field, H . When E,IkT 2 2
and H M i l 2 K & 0.4,the relaxation time is well approximated by

1) Now a t Groupe de Transitions de Phases, C.N.R.S., Grenoble.

230 J. M. D. COEY and D. KHALAZALLA

ML is the saturation magnetization per unit volume a t a temperature T.yo is

-
the gyromagnetic ratio, and E , is the energy barrier t o rotations of the moment
(EB IKI V ) . The application of a field comparable t o KIM; reduces t. Cal-
culations for cubic anisotropy show that z is not a monotonic function of T ,
and (1) does not apply when E B / k T x 1 [2].
Besides the fluctuations of the net moment of a particle, there are the fluc-
tuations of individual ionic moments caused by spin-spin and spin-lattice
interactions. These will be represented by a relaxation time 7 ' .
Superparamagnetic behaviour is often inferred from the magnetization curve
of particles which are small enough t o be single-domain [3]. It should be a func-
tion of H I T , and there should be no hysteresis or remanence. I f the pai%icles
all had the same moment, rn, then the magnetization of a non-interacting
assembly would be given by the classical Langevin function

M = M s [coth (g)
g] -

if the effects of shape and anisotropy are negligible.

A difficulty in relating ( 1 ) or (2) t o experimental observations is that it is
impossible in practice t o produce ultra-fine particles which all have the same
volume and shape, and even if it was possible, they would not necessarily all
have the same magnetic moment. Two reasons for the existence of a range of
magnetic moments in fine antiferromagnetic particles were given by N&J [4],
and the same arguments can be applied t o ferrimagnets. However, in il real
ferrimagnetic sample the range of moments will be mainly due t o the inevitable
range of particle size.
The magnetic properties of very small particles of y-Pe,O, have been studied
by several workers [5 t o 71. The critical size for spherical y-Fe,O, particles t o
be single-domain has been calculated by Morrish and Yu [5] t o be 1000 A.
Berkowitz e t al. [7] found t h a t acicular y-Fe,O, is superparamagnetic a t 293 OK
if the particle size d <400 A. Their materials all showed coercivity, even when
the average crystallite size was 50 A, which suggests a very broad distribution
of particle size or shape.
I n the Mossbauer spectra of ultra-fine particles, superparamagnetism is
characterized by the collapse of the hyperfine splitting and the appearance of
a central peak because z is less than the Larmor precession time for the nucleus
in the hyperfine field [8]. I n static magnetization measurements, a material is
considered superparamagnetic if z does not exceed the time constant of the
instrument, usually 1 t o 10 s, whereas in Mossbauer measurements on 57Fe,
a n oxide is superparamagnetic if z 6x s. These two criteria are not
completely disparate because z increases exponentially with volume (1). It is
customary t o define a blocking temperature, T,, for a particle, a t whirl1 z is
equal t o the characteristic time of the measurement.
Mossbauer studies have previously been made of superparamagnetism in the
ferrimagnetic spinels Fe,O, [91, Co,O, [lo], Fe,S, [111, MgFe,O, [121, and NiFe,O,
[13]. The latter authors showed that it was possible t o partially restore the
hyperfine splitting by applying a 17 kOe field a t room temperature to a sample
with d = 97 A.
I n this article we describe magnetization and Mossbauer measurements on
ultra-fine particles of y-Fe,O,. A much greater variety of information about the
magnetic properties of the particles can be obtained when they are studied by
 Superparamagnetic y-Fe,O, 231

both techniques than is available from either one, separately. Specifically,

we compare several methods of determining the particle sizes, discuss surface
effects and the possibility of nonmagnetic y-Fe,O,, and suggest an explanation
for the Mossbauer spectra of superparamagnetic particles in a n applied field.
A preliminary note on one of the results has already been published [14].

2. Experimental Procedure and Results

2.1 Sample preparation and identification
The material was prepared from a mixture of equal volumes of 0.04mol
-
FeC1, 6 H,O and 0.02 mol PeCl, 4 H,O solutions. 500 ml of the mixture was
heated t o 40 "C and stirred vigorously while 0.05 mol NaOH was added t o give
a black precipitate which was then filtered and washed. After drying in air, the
powder turned dark-brown. It was examined in the electron microscope, and
consists of agglomerates, lo3 t o lo4 A in diameter, one of which is shown in
Fig. 1. The agglomerates appear t o be made up of smaller grains, not markedly
acicular, with a diameter of 50 t o 75 A, and these grains are taken t o be the
superparamagnetic particles. The pictures support the view that ferric gels
are flocculated colloids, composed of crystalline particles formed directly from
solution.
The compound was identified as y-Fe,B,fromthe Debye-Schemer X-ray pattern
and the Mossbauer spectra described below. The powder pattern showed eleven
broad reflexions which correspond t o the most intense spinel-structure lines of
either Fe,O, or y-Fe,O,. An apparent crystallite size of 74 A was inferred from
the line broadening.
The weight per cent of iron was found by chemical analysis t o be 56.9 wt%
and no Fe2+was detected. Iron is 69.9% by weight in the formula Fe,O,. This
discrepancy is discussed in 3.1.
2.2 Magnetization measurements
Static magnetization measurements were made in fields up t o 18 kOe in the
temperature range 4.2 t o 296 "K, using a vibrating-sample magnetometer with

Fig. 1. Electron micrograph of the ultra fine y-Fe,?, par- Fig. 2. Coercivity of y-Fe,O, as a function of tem-
ticlrs. The superparamagnetic particles have dimensions of perature; ( x ) 955 A spherical particles,( 8 )ultra-
the order l o a A, and are bound together in agglomerates fine particles
with dimensions l o s t o lo4 A
 J. M. D. COEY and D. KHALABALLA

Fig. 3. Ratio of the remanence to the saturation magneti-

zation, extrapolated to 1/H = 0 for y-Fe,O,; (x) 955 A
particles, ( 0 )ultra-fine particles

I l l I l HlkOei- L_
Fig. 4. Magnetization curves for ultra-fine y-Fe,O, particles
at 77 and 296 "K. The dashed line is the fit using the size
distribution of Fig. 9
0 2 4 8 12
H(k0e) ---
16

a time constant of about 1 s. The saturation magnetization, M s ( T ) was ob-

tained by extrapolating t o 1 / H = 0. The same value, 59 e.m.u./g, was found
for the ultra-fine particles a t any temperature between 4.2 and 80 OK, the
magnetization in 18 kOe being about 10% lower than the extrapolated value.
At room temperature, Ms(296) = 50 e.m.u.lg. Ms(296)/Ms(0)= 0.85. For
comparison, we will use data on spherical y-Fe,O, particles with a mean diarncter
of 955 A, a third of them larger than 1000 A , for which M,(O) = 80 e.m.u./g
and Ms(296)/M,(0) = 0.90 [l5].
The temperature variation of the coercivity, H,, i s shown in Fig. 2 for both
the ultra-fine particles and the 955 A spheres. Fig. 3 shows MR(T ) / M , ( 5") for
the two materials, where MR is the remanence. Above 200 "K, the magnetiza-
tion curve of the ultra-fine y-Fe,O, shows no hysteresis, hence T, for all the
particles in the sample is less than 200 OK. An upper limit to the size o f the
particles, and the complete size distribution will be calculated from the data of
Fig. 3.
The magnetization curves for the ultra-fine particles a t 77 and 296 OK are
shown in Pig. 4. They are quite different from those for the larger particles,
which rise much more steeply when H & 2 kOe, and then approach saturation.
A variety of information about the particle-size distribution will also be deduced
from the room-temperature magnetization curve. It should be noted that, a t
room temperature, the ultra-fine particles are entirely superparamagnetic. and
a t 77 OK, 90% of them are still above their blocking temperature for magneti-
zation measurements.

2.3 Mossbauer measurements

Mossbauer spectra have been obtained for both the ultra-fine and the 955 A
y-Fe,O,, with and without a n applied field of 50 kOe. The experimental ar-
 Superparamagnetic y-Fe,O, 233

I I I I I I I I I I I I I
-12 -8 -4 0 4 8 12
veloci&{mm/s) -
Fig. 5. Mossbauer spectra of ultra-fine y-Peso, particles at 296 OK. a) without and b) with an applied field of
5 0 kOe. The dashed line is the calculated spectrum, explained in Section 3.3

rangement with H parallel t o the y-direction is illustrated elsewhere [l6]. At

room temperature the superparamagnetic material gives a broad, triangular
absorption peak which is similar to the spectrum calculated by van der Woude
and Dekker [17] and Wickman [lS] for z = 2 x s. When the field is applied,
the spectrum changes completely, t o two broad partly overlapping hyperfine
patterns, as shown in Fig. 5.
When a large magnetic field is applied t o bulk y-Fe,O,, the two overlapping
hyperfine patterns arising from ferric iron in the antiferromagnetic-coupled A
and 33 sites are resolved [19, 201 because, when the net moment is aligned with
the applied field, the A-site hyperfine field is parallel and the B-site hyperfine
field is antiparallel t o H .
The resolution of the six-line hyperfine pattern of the 955 A y-Fe,O, a t 296 OK
into two four-line patterns corresponding t o Fes+ in the two sites is shown in
Fig. 6. The Mossbauer spectra below room-temperature without and with the
field resemble those a t room temperature.

-12 -8 -4 0 4 8
velocity (mm/s)-
Fig. 6. Mossbauer spectra of 955 A y-Fe,O, particles at 296 O K . a) without and b) with an appliedfield of 50 kOe
234 J. M. D. COEY and D. KHALAFALLA

Wig. 7 . Nossbauer spectra of ultra-finey-Pe,O, particles a) a t 80 "E and b) and c ) a t 5 "E without and a I t l i an
applied field of 50 kOe

I n order t o compare the spectra of the two samples, it is necessary t o cool

all the ultra-fine particles t o a temperature where relaxation effects are un-
important. Spectra of the ultra-fine particles a t 80 and 5 OK are shown in Fin. 7 .
At 80 OK there is no sign of the central peak, and the spectrum has become a
six-line pattern with broadened, asymmetric lines. The sample has ceased t o
be superparamagnetic in the Mossbauer measurement a t 80 OK although most
of it remains so in the magnetization measurement because of the longer charac-
teristic time. On cooling t o 5 OK, the lines become narrower, but remain asym-
metric, and a little broader than for the larger particles.
Application of a 50 kOe field gives rise t o a spectrum which is almost the 9'dine
as the one in Fig. 6b. The spectrum splits into separate Fe3+ (A) and Fe3- (B)
patterns with effective fields of 558 and (486 f 5) kOe, and the intensity ratio
measured from the areas of the elements of the first line, is 1 :( 1.71 & 0.05). The
ratio for 955 A particles a t the same temperature is 1 :( 1.67 & 0.04). The tlif-
ference between the spectra of Fig. 7 c and 6 b is that lines 2 and 5 are not
completely removed by the high field. The intensities of the outer and iiiner
pairs of lines vary as (1 +
cos2 O ) , whereas those of the middle pair (2 ant1 5),
arising from AM = 0 transitions, vary as sin2 8. 8 is the angle between the
hyperfine field and y-ray direction.
Bulk y-Fe,O, is saturated in an applied field of a few kOe, 8 0 for both
sites, and a ratio of 3.00:0.00:1.01 is found for the areas of the three pairs,
whereas the ratio is 3.00:0.69:1.08 for the ultra-fine particles in both 25 and
50 kOe. The error in the second part of the ratios is less than 0.10. This
means t h a t some or all of the ionic spins are canted from the direction of
the stable net moment. I n similar particles, it was found that lines 2 and 5
persist with nearly the same intensity in a field of 90 kOe [21].
The spectra of Fig. 7 show t h a t the compound is certainly y-Fe,03, and not
Fe,O,. Magnetite gives a quite different spectrum, both above and belox the
Verwey transition.
 Superparamagnetic y-E"ezO, 235

3. Discussion
3.1 Saturation magnetization
I n most samples of bulk y-Fe,O,, the value of Ms(296),extrapolatedt o l/W=O,
is usually in the range 70 t o 75 e.m.u./g, but values o f 35 to 60 e.m.u./g are
found for superparamagnetic samples. Berkowitz et al. [7] explained the dif-
ference by proposing that a large fraction of the y-Fe,O, is in non-magnetic
grain boundaries, but such an explanation is not supported by our observations.
I n our material, a quarter of all the iron would have t o be in the grain
boundaries, and there would be a pronounced central peak in the Mossbauer
spectrum a t all temperatures. As there is no sign of any central peak in the
spectra a t 80 and 5 OK it can be asserted that, a t most, 1%of the iron ions
lie in such grain boundaries.
Other explanations of the low moment must be found, and there seem t o
be two possibilities, which will be discussed in turn. Either the cation or spin
arrangement in the ultra-fine particles is different, and gives a lower net moment
than in the bulk material, or else the samples contain a large fraction of a non-
magnetic, non-crystalline substance in addition t o y-Fe,O,.
The formula of Fe,O, is often supposed t o be
+ ) 01/31 0;- ,
( ~ e ~[F~E; (3)
where the different brackets denote A and B sites. There is also evidence for
the existence of another phase containing hydrogen [22,23] which is represented
as
(Fe3') [FeiJ H&]O?- or (Fe3+)[Fe;; u$j OHGz 0;i . (4)
The weight per cent of iron in (3) and (4)is 69.9 and 68.4 wt%, respectively,
but the main difference is in their magnetic moment.
I n this section, only magnetic moments a t IT = 0 will be compared; the dif-
ferent temperature dependence of the magnetization of the two samples will
be considered in Section 3.3.
The spin-only moments corresponding t o (3) and (4) are 87.4 and 68.4 e.m.u./g.
The moments of 76 t o 82 e.m.u./g usually found in butk samples of y-Fe,O, cor-
respond more closely t o (3) than t o (4) although they may be mixtures of both
phases [24]. Our superparamagnetic sample has a moment of 59 e.m.u./g. Part
of the low moment could be explained if our material was actually the hydrogen
phase (4),but this possibility is also ruled out by the Mossbauer data.
The cation distribution can be determined from the areas of the spectra arising
from iron on the two sites. Provided the absorber is thin and the temperature
low [25], the area of the spectrum is proportional t o the number of iron nuclei
contributing t o it, and the Fe3+(A):Fe3+(B)area ratio is the same as the cation
ratio. The observed area ratio, 1 :( 1.71 & 0.05) is consistent with 1 : 1.67 expected
for (3). If any of the hydrogen phase was present, the ratio would be reduced
towards 1 : 1.50.
Although there is nothing in the Mossbauer spectra t o suggest non-magnetic
grain boundaries or a n unusual cation distribution, it is clear t h a t the spin
arrangement in the ultra-fine particles differs from that o f the bulk material.
The spectrum of Fig. 7 c could be interpreted as indicating that all the cations
make a n average angle of 32" with the applied field, or else 34% of them make
random angles between 0 and 90". I n both cases there will be a reduction of
1 5 t o 17% in the moment.
236 J. M. D. COEY and D. KHALAFALLA

I Fig. 8 Infra-red absorption spectra a) of ultr.i-fine

particles and b) of 955 A y-Fe,O,

I
05 1 I
I
b ' 0 - 1 I , I I I I I ~ ~ I I I
4m 3m 2000 721~ m aoo ti00 4oo
~

frqumcy (cm 'I

The other reason for the low moment is water adsorbed onto the partirle
surface. The evidence is as follows: in the first place, the iron content of the
samples is much lower than expected for (3), even though the cation distribution
is consistent with this formula. When samples were heated a t 200 "C for sevcral
hours, they suffered an 8% weight loss, but after cooling, they gradually returned
t o their original weight. Furthermore, there are strong absorption bands a t
3400 and 1550 cm-l, in the infrared spectrum of the ultra-fine particles, which
are virtually absent in the larger crystallites. These spectra are shown in Fig. 8.
Bands characteristic of H,O or OH-, were still present, even when the ultra-fine
particles had just been heated a t 200 "C. Since there is no absorption in the
range 800 t o 1200 cm-l where the characteristic OH- deformation usu,dly
appears, we conclude t h a t the y-Fe,O, crystallites are coated with a few layers of
water molecules, comprising 18.5% by weight, so that 56.9 wt% of the sample
is Fe.
From the observed cation and spin distribution, the moment of the y-Fe,O,
itself should be (76 7 ) e.m.u./g. This value is reduced by water to (63 f
& 5) e.m.u./g in agreement with the 59 e.m.u./g measured.
3.2 Pavticle-size distribution
There are three possible ways of obtaining information about the particle
sizes in a superparamagnetic sample from magnetic measurements [3]. The first
is t o fit the M ( H ) curve t o a Langevin function, the second is to use the ME/'Mh
curve t o find the ferrimagnetic fraction as a function of temperature, and the
third uses the fact that M s falls more rapidly with T for small particles which
have a large surface t o volume ratio, hence a lower ordering temperature.
The best fit of (2) t o the room-temperature magnetization curve was found
by the method of least-squares. It gives m = 0.35 x 10-ls e.m.u., corresponding
to a sphere of diameter 65 A, with the measured saturation magnetization.
The density of y-Fe,O, is taken as 4.79 g/cm3. A better fit can be obtained with
a range of particle sizes. The result, with a uniform distribution of m between
0 and 1.05 x e.m.u./g is shown in Fig. 4 and 9 by the dashed lines. It is
a great improvement over a simple Langevin function. The sizes of the larger
and smaller particles present in the sample may also be estimated from two
limits of (2). When H --+ 0 , M -+ M s (m H / 3 kT).The initial susceptibility is
mainly determined by the large particles in the assembly. From the initial
slope of the 296 OK data, shown in the inset in Fig. 4, we find that m = 1.15 x
X1O-l6 e.m.u., giving d = 97 A. On the other hand, as H-+ 00, M -+
 Superparamagnetic y-Fe,O, 237

+Ms (1 - k T / m H ) . The slope of M ( l / H )in high fields is mainly determined

by the smaller particles in the assembly, because the larger ones are already
saturated. From the slope, we find m = 0.17 x 10-1O e.m.u., and d = 51 A.
The second way of obtaining information about the particle size uses the
data of Fig. 3 t o find the temperature variation of the superparamagnetic
fraction. At any given temperature, the critical volume for superparamagnetism
in static magnetization measurements can be calculated by setting z = Is in ( I ) ,
provided t h a t E , is known. E , is related t o the anisotropy, and depends on
whether the moment reversal is coherent or not. Either crystalline, shape or
strain anisotropy may predominate in these particles, but we set E , = K( V ) ,
and use the z deduced from the room-temperature Mossbauer spectrum to find
a n effective anisotropy constant, K . ( V ) is the average particle volume,
taken as 0 . 2 ~ cm3. With z = 2 x loe9s and T = 296 OK, ( 1 ) gives
K = 1.2 x 106erg/cm3. Since this is much larger than the values of the crystal-
line anisotropy constant, K,, usually found in spherical particles of y-Fe,O,
[26, 271, the source of the anisotropy is almost certainly different in the ultra-fine
particles and in the bulk material. Interactions between crystallites, which
may be considerable in the agglomerates, will also tend t o increase K . Never-
theless, regardless of its physical interpretation, once ( 1 ) has been used
t o deduce a n effective anisotropy constant from a particular z and T , it is pos-
sible t o generate consistent solutions for other values of z and T , provided K
does not depend much on temperature. Evidence is given in Section 3.3 to
show t h a t this is true.
The maximum particle size, corresponding t o a blocking temperature of
200 “K in the magnetization measurements, is 106 A.
The complete particle-size distribution, determined by taking the ratio of
(M,/Ms) for the ultra-fine particles t o that for the 955 A particles as the ferri-
magnetic fraction, is plotted as a solid line in Fig. 9. The average particle
volume for the distribution is 0.11 x om3, corresponding t o d = 59 A.
When plotted as a function of d , the distribution is peaked about 58 A, and the
range a t half-maximum is from 30 t o 72 A.
Although ( M E / M s )a t 4.2 OK does not come close to 0.866 or 0.5, the values
expected for single-domain particles with cubic or uniaxial anisotropy [28],
it approaches the same value a t low temperatures as it does for the 955 A par-
ticles. These particles are partially multidomain [161, and interactions between
the ultra-fine particles are likely t o give the agglomerates some multidomain
character. The comparison is a little arbitrary but the distribution obtained in

2040050 60 70 80
dfa) -

Fig. 9 . Particle size distributions, __ deduced I

for the M R / M s curve of Fig. 3, and - ~ ~- - used I I
a
t o fit the M ( 2 9 6 ) curve of gig. 4 a1 a2 03 a4 a5
v(~o-’8cm3) -06
238 J. M. D. COEY and D. KHALAEALLA

Table 1
Size of the ultra-fine y-Fe,O, particles, determined b y several methods

no. method section d (4

Direct observation in electron microscope 2.1 = 50 to 75
X-ray powder-line broadening 2.1 74
Room-temperature magnetization curve 3.2
a ) large particles: low-field slope 97
b) small particles: high-field slope 51
c) best fit: single size 65
d) best fit: range 0 t o 94
mean 72
Temperature dependence of reduced remanence 3.2
a) maximum particle size 106
b) range at half maximum 30 t o 7 9
c) mean particle size 59
Temperature dependence of saturation magnetization 3.3 66

this way is consistent, with the information obtained from the magnetization
curve. All the results on the particle sizes are tabulated in terms of d in Table 1.
The third method is discussed below.

3.3 Miissbauer spectra

A condition for observing a n unbroadened Mossbauer spectrum is that
< r
E 3 2 M c2 I'. E , is the energy of the nuclear transition, is the natural line-
width, and M is the mass of the grain in which the absorbing nucleus is bound
~91.
For 67Fethe condition becomes M > 4 x 1O-l' e.m.u./g, and the correspond-
ing diameter of a grain of y-Fe,O, is 250 A. Since we observe a sharp Mossbauer
spectrum a t 5 OK for the ultra-fine particles, none of which have even a ttmth
of the minimum mass, they cannot be free t o recoil independently. They nriist
be coupled together by van der Waal's forces, or by interstitial water, into
much larger grains which are probably the agglomerates shown in Fig. 1.
The Mossbauer spectra in Fig. 7 all show some assymetric line broadening.
Some broadening is t o be expected, even in large particles of y-Fe,O, if they
have no vacancy superstructure. An A-site in (3) has ten B-site superexchange
neighbours, but if the vacancies are distributed a t random, environments 11 ith
8 t o 12 occupied neighbouring B-sites have a significant probability. These
different environments give rise t o a range of dipolar and supertransfei.ied
hyperfine fields a t the A-sites. However, the outer lines in Fig. 7 a and b are
0.2 and 0.7 mm/s broader than usual for y-Fe,O,. There may be some broadening
due to surface effects and t o the size of the agglomerates absorbing the recoil
momentum. Furthermore, a t 80 "K there will be a contribution from the smallest
particles in the distribution which have a short relaxation time and a low magnet-
ic ordering temperature.
I n ultra-fine particles, a significant fraction of the ions are in the surface lager.
The two distributions shown in Fig. 9 have 42 and 30% of the iron ions in the
surface. Van der Kraan [30] has recently shown t h a t the surface ions in ultra-
fine particles of u-Fe,O, have a shorter spin relaxation time or a smaller net
magnetic moment than the interior ions, and their recoilless fraction decreases
 Superparamagnetic y-Fe,O, 239

more rapidly with temperature. It is interesting, then, t h a t the spectrum a t

5 O K is so similar t o t h a t of the bulk material. I n particular, the hyperfine
field of the surface ions can differ b y no more than 7 % from t h a t of ions in the
interior. It is also t o be expected that they should have a larger quadrupole
interaction, and t h a t their spectrum be broadened because of the range of
electric field gradients a t sites near the surface, but this effect may be reduced
by the surface coating of polarizable H,O.
I n order t o explain the room-temperature Mossbauer spectrum in the 50 kOe
field, two effects will be taken into consideration :
1. The particles have a range of magnetic moments, and so the field induces
in them a range of magnetic polarization, M / M s for the various particles in the
distribution being given by (2). Regardless of how rapidly the orientation of
a particle may change with respect t o the applied field, a hyperfine field propor-
tional t o the net polarization of an ion in the course of a Larmor precession time
will be experienced by the nucleus. The superparamagnetic relaxation time is
less than tL without a field, and is expected t o decrease further when the field
is applied. Hence the polarization in a time zLis given by the Langevin function,
and provided z’ <zL, the moment m has a temperature dependence like t h a t
of a stable, single-domain particle.
2. M s a t 296 OK is not likely t o be the same for all particles, because the
smaller ones will have lower ordering temperatures. The ordering temperature,
T , , will be approximately given by

where N is the number of magnetic ions in the particle, N , of which are in the
surface. Thus M s , and the hyperfine field for a polarized particle, will be
reduced compared t o the bulk material. At low temperatures, this effect is
unimportant, but a t room temperature it produces more line broadening than 1.
The size distribution of Fig. 9 (solid curve) has been used t o calculate the
Mossbauer lineshape expected for the ultra-fine particles in a 50 kOe field,
allowing for the ranges of polarization and ordering temperature. The positions
ofthe Mossbauer resonances for the largest particles in the distribution are taken
from the spectrum shown in Fig. 6b, but the persistence of lines 2 and 5 is also
taken into account. Satisfactory agreement is obtained between the calculated
spectrum, shown by the dashed line in Fig. 5 b, and the experjmental point,s.
I n principle it is possible to deduce the particle-size distribution from the
behaviour of M s (T) in the vicinity of the magnetic-ordering temperature,
provided that the dependence of T , on d is known.
I n fact y-Fe,O, converts t o u-Fe,O, below T,, but some estimate of the average
size can be obtained by comparing thevalues of M s ( 2 9 6 ) / M s ( 0for
) the ultra-fine
particles and the bulk material, and deducing the reduction of ordering temper-
ature (16%) expected for the former. Assuming the simple relation between size
and ordering temperature given by ( 5 ) ,a value of d = 66 A is obtained. The
agreement with the other particle-size determinations may be taken as a justi-
fication of ( 5 ) and, consequently, the calculation of the Mossbauer lineshape.
It should be pointed out that there is nowhere any sign of larger hyperfine
fields in the ultra-fine particles than in the bulk material. Hence z’ < s.
This may be compared to the spin-spin relaxation time of 1.2 x 10-lo measured
in single-domain y-FeZO, particles [ 2 7 ] .
240 J. M. D. COEY and D. KHALAFALLA

Two interpretations of the spectrum a t 5 OK in the applied field were suggested

in Section 3.1. It is emphasised t h a t the particles are stable and t h a t the spec-
trum in the 50 kOe field cannot be explained by a lack of saturation due t o
anisotropy. The effective anisotropy constant deduced from the room-temper-
ature Mossbauer spectrum is more than an order of magnitude too small t o
explain the observations. It may be seen in Table 1 that the average part,icle
size deduced from (1) and the temperature variation of M , / M , is somewhat
smaller than that found by any of the other methods, so the effective anisotropy
decreases with temperature. The interpretation likely to be closest t o the truth
is that 34% of the iron ions, lying in the surface layer, are canted a t angles
between 0 and 90" to their spin direction in the bulk material.
The percentage is consistent with the percentage in the surface layer deduced
from the distributions of Fig. 9, and such canting can arise naturally from
competing inter- and intra-sublattice exchange interactions. Ions in the surface
layer will have various numbers of magnetic neighbours on A- and B-sublattices,
and they are analogous t o the magnetic ions in diamagnetically substitutetl fer-
rites. Canting has been observed, for example, in zinc-substituted nickel ferrite
[31, 321. However, there is also likely t o be some canting of the spins in the
interior of the very smallest particles, because of the high random concen-
trations of vacancies.
4. Conclusions
From a comparison of Mossbauer and magnetization measurements of ultra-
fine crystallites of y-Fe,O,, we have shown that superparamagnetism is a func-
tion of the measuring time. Several proposed explanations for the low moment
could be rejected on inspection of the Mossbauer spectra a t 5 OK, and the
moment per gram is actually reduced by absorbed water and a non-collinear
spin arrangement. It is likely that the particles have a core with much the
same cation and spin arrangement as bulk y-Fe,O,, and a surface layer in which
the iron spins are canted from their usual direction. Several layers of water
molecules cover the surface. The same description will probably apply t o any
magnetically ordered compound with competing exchange interactions, and
the saturation magnetization will be appreciably reduced in particles whose
diameter is less than about 200 A.
A good measure of agreement was obtained among five independent methods
of determining the particle sizes, and the size distribution was determined using
both magnetization and Mossbauer data. The Mossbauer spectrum of super-
paramagnetic particles in a large applied field could be explained on the basis
of this distribution, taking into consideration the magnetic polarization of the
particles by the field, and their range of ordering temperatures.
Acknowledgements
We wish t o thank Professor A. H. Morrish for some helpful comments. This
work was supported by the National Research Council of Canada, t o which
each of the authors is grateful for a postgraduate scholarship.

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(Received February 2, 1972)

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