Magnetic Properties of Some Ferrite Micropowders

A. E. Berkowitz and W. J. Schuele

Citation: J. Appl. Phys. 30, S134 (1959); doi: 10.1063/1.2185853

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 JOUR:-tAL OF APPLIED PHYSICS SUPPLEMENT TO VOL. 30. NO . " .\PRIL, 1959

Magnetic Properties of Some Ferrite Micropowders*

A. E. BERKOWITZ ,\NO W. J. ScHUELE
TIll: Franklin Institute Laboratories, Philadelphia 3, Pennsylvania

Micropowders of stoichiometric copper, nickel, and cobalt ferrites were prepared by low temperature
«800°C) treatment of the coprecipitated metal oxalates. The magnetic properties of each ferrite were
determined as functions of particle or crystallite size in the range from 70 to > 2(K)() A. Particle sizes were
determined from x-ray line broadening and from electron micrographs.
The micropowders exhibited superparamagnetic, single domain, or multidomain behavior depending on the
particle size. The critical size for single domain behavior, depending on composition, was between 300 and
700 A. In this size range, high coercive fo rce and remanence were obse rved in spite of appreciable sintcring of
the particles in some cases. The remanence values and the magnitude and temperature dependence of the
coercive force indicated that magnetocrystalline anisotropy determ ined the properties of the single domain
particles. The magnetic properties of the very small particle size samples showed the large temperature
dependence characteristic of superparamagnetism.
Quenched and slowly cooled copper ferrite micropowders were prepared with similar particle sizes. The
remanence and coercive force of the quenched samples were much lower than those of the slowly cooled
samples. This indicated different critical sizes in these two types of copper ferrite. This could be due to the
difference in either the moments or the magnetocrystalline anisotropy.

PREPARATION AND EXPERIMENTAL PROCEDURE broadening and from electron micrographs. When indi
vidual particles could be distinguished on the micr
N I CK EL, cobalt, and copper fe rrite micropowders
were prepared by the thermal decomposition of
the co-precipitated metal oxalates. Lower tempe ratu res 1
graphs, thei r sizes generally agreed with the line
broadening determinations. Scanning with an x-ra
diffractometer indicated that all samples had the proper
,tre required than in the usual methods of ferrite pro-
stoichiometric ferri te structure. Saturation magnetiza.-
duction because, in the ideal case, the oxalate particles
tion an d Curie temperatu re measurements were in good
are solid solutions of both metal ions, and diffusion
agreement with published values.
distances are small. X-ray analysis l showed that the
The magnetic data to be discussed, coercive force
nickel-iron and cobalt-iron oxalates were solid solutions,
(H ,) and remanence/ saturation (I H/ l s), were obtained
but that the copper and iron oxalates precipitated sepa-
from hysteresis loops of samples packed in al uminum
rately. Presumably, this is due to a greater mismatch in
cylinders Cl in. long X t in. diameter). The hysteres·
atomic radii between copper and iron. Generally, the
loops were plotted by a dc hysteresigraph at 77' and
decomposition of the oxalates to the fer rites could be
300'K in maximum fields of 12 ()()() oe.
accomplished by heating in ai r between 400° and 800°C
for four hou rs.
Decomposition in ai r produced sintered aggregates of
ferrite particles or crystallites. The degree of sinteri ng The data for some nitkel fer rite micropowders are
and the ave rage crystallite size depended on the tem- shown in Table 1. For the first five samples with
perature and annealing time. A range of particle sizes crystallite sizes increasing from 105 to 172 A, it is seen
>300 A were produced in this manner. Particles <300 A that both He and I RI I s increase considerably between
were prepared by decomposing the oxalates in molten 300° and nOK. This tempe rature dependence is charac..
KN0 3 • Particle sizes were determined by x-ray line te ristic of superparamagnetic particles. Thus the par. .
tides in this size range are mixtures of supe rparamag..
TABI.E 1. l)roperties of Ni Fe Z04 micropowders. netic and single domain particles. It is noted that fh
tempe ratu re dependence decreases with increasing c1)'5"'
{Rl ls - fl.(oe)-
CrrSl:lllite
size ( A ) 300° 1\: j j 0 i( 300 0 K 17° K
tallite size, indicating the presence of larger concen·
trations of single domain particles. Since the crysta1lite
105 0 0.23 0 182
125 0 0.38 0 442 sizes are averages, they would suggest that the critical
125 0.08 0.34 56 313 size for single domain behavior was the order of 300 A.
132 0. 14 0.35 104 312 For the last two samples with crystalli te sizes of 507
172 0.21 0.34 104 260
50i 0.35 0.35 156 In and 64-+ A there is a rather small temperature depend-
f>I4 0.29 0.31 114 156 ence of fI e and I RI I s. Furthermore, Heat 77°K is
smaller than for the first five sam ples. This suggests that
-At 11 - 12 000 oc. these last two samples are mixtures of si ngle and
• This research was supporled in whole or in part by the U. S. multidomain particles. They also suggest a critical single
Air Force under Contract No. AF 33(616)·504 1, monitored by the domain size of ~300 A.
Aeronautical Research Laboratory, Wright Air Development Th e largest coercive forces are of the order of
Cen ler.
I W. J. Schuele, J. Phys. Chem. 63 , 83 ( 1959). Kil l s (K1 = magnetocrystalline an isotropy coefficient,
1345

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 MAG NET 1 CPR 0 PER TIE 5 0 F SO M E FER R 1 T E M 1 C R 0 PO IV D E R 5 1355

_saturation magnetization); namely, 230 De at T ABLE III. Propert ies of quenched (Q) and furnace cooled (F .e.)
eu Fe 204 micropowders at 77 QK.
j K and 320 De at 77 °K . Th is suggests a coercive
ree for the single domai n particles of the order of Crystallite si~e (A) Il «oc)-
oKl/ I s, which is unlikely for a rando m array of single F.C. Q F.e. Q
main particles. T herefore, it is possible that a certain 200 128 0.55 0.46 1720 no
ount of shape anisotropy exists in these pa rticles. 505 501 0.53 0.33 1220 2i6
485 470 0.56 0.31 1020 286
Co Fe 20 4 520 483 0.55 0.26 1120 156
>2000 >2000 0.42 0.2 6 650 141
The data for some cobalt ferrile mi cropowders are 520 >2000 0.13 0.21 290 115
ibown in Table If. It should be no ted that most of the
e! crystallite size samples were not saturated in - At H - 12 000 oc.

JlBId. of 12 000 oe, especially at 77°K. Thus, t he values

for He are somewhat lower, and I ni l s is higher than
wou1d be obtained with saturating fields . This is true to Copper ferrite samples were prepared by decomposing
areater exten t for the nOK data than for the 300 0 K th e oxalates in air for 16 hr at temperatures from 600° to
ta.. The inability to saturate was made strikingly 1100'C. At the end of each annealing period, part of the
Mdent by the fact that, at 12000 DC, I s was larger at sample was quen ch~d; anothe r part was furnace cooled .
. than at 77°K for all except the last two samples. The tetragonal structure was obtained for the furnace
It is noted in T able II that there is an appreciable cooled samples and fo r the samples quenched from
below BOO°C. A cubic structure was oblained for the
TABLE II. Properties of Co F e~O. micropowders . other qu enched samples. The previously observedl in-
crease in satura tion magnetization was obtained on
IR(IS~ ll «oe)-
30Q C K no r.;: JOOOK 77°1( quenching.
In Table III arc shown t he data for both types of
72 0.06 0.31 104 3130
84 0.t6 0.29 41i 3340 samples. V-li th the exception of th e llOQoe anneals, the
120 0.22 0.33 440 2800 crystallite sizes are similar fo r both types of treatment
355 0.55 0.84 2080 6900 at each temperature. In view of the simi la r crystallite
459 0.48 O.St 1200 4570
1()(' 0.51 0.86 1580 6930 sizes, it is very in teresting to note that He and 1 u/ l s are
1()(' 0.56 0.91 1053 5450 always smaller for t he quenched samples. This implies a
1030 0.52 0.84 738 4240
>2000 0.24 0.88 267 2290 d ifferent critical single domain size which could arise
from the difference in I s or K! . I t is only possible to say
a"\t 11 ",12000 oe. that the quenched samples contain a smaller concen-
tration of si ngle domain particles. Also, in th is case, the
~mperature dependence of H, and J RI I s for all
values of I n/Is are not the saturated values. The
samples. However, elimination of the saturation prob-
cri tical single domain size appears to be between 300
lem. discussed above would redu ce th e difference behveen
li/ l sat 77° and 300 0 K for the la rger crystallite sizes and 500 A.
to a greater exlcn t than for the smallest ones. Therefore, Tak ing the published value 4 for K l at 77°K and the
the £mallest crystallite size samples exhibit a super- accepted value for J s, K ,I J s= 1250 oe. The la rger
paramagnetic behavior. For the la rge r crystallite sizes, coercive forces are of this magnitude. Using the value of
the saturated value of J RI rs would be reduced but 1 s pu blished with the an isot ropy data, K, I rs= 650 oe.
would still be >0 .5 for some of the samples. This H owever, considering the general magni tude and tem-
indicates that magnetocrystalline anisot ropy dominates perature dependence of the coercive force, it seems li kely
the behavior of the cobalt ferri te micropowclers. The that magnetocrystalline anisot ro py is the dominant
evidence from T able II is that the critical si ngle domain an isotropy.
size is of the orde r of iOO A. A complete report of these experimenls will be
'. KJI s is approximately 6000 oe at 300 0 K and 2 or 3
published in the future.
timei this value at li oK. The highest coercive forces
obtained at these temperatures are 2000 oe and 7(x)(} oe,
respectively. Neel's2 exp ression for this case, Ifc =O.M. ACKNOWLEDGMENTS
K,jI 8 , would give .j000 De at 300'K , and 8000 -> 12 000 We are grateful to ~Ir. Robert Grieger for making the
De at 77°K. This would be in reasonable agreement with magnetic measurements. \Ve appreciate useful discus-
the iuggestion of large concent rati ons of single domain sions with Dr. Henri Amar.

----
~iclesJ with magnetocrystalline anisotropy domi -
nating. l For example, R. Pauthenct and L. Bochirol, j. phys. radium
12,2-19 (1951 ).
21. Neel, Complo rend. 224 , 1488 (194i ). 4 T. O. Kamura and Y. Kojima, Phys. Rev. 86, 10·10 (1952 ).

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