Spinel Compounds: Structure and Property Relations

Journal

J. Am. Ceram. Soc., 82 [12] 334246 (1999)

Magnetic Properties of Ordered and Disordered Spinel-Phase Ferrimagnets

Matthew A. Willard, Yuichiro Nakamura,*, David E. Laughlin, and Michael E. McHenry
Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213

In spinel-phase ferrimagnets, disorder in the cation distribution between octahedral and tetrahedral sites can influence such fundamental magnetic properties as saturation magnetization, exchange coupling, and ferrimagnetic ordering temperatures. Given the sensitivity of magnetic properties to structure, it has been suggested that magnetic properties may be used as a probe of disorder in ferrimagnetic spinels. In this article, we review the fundamentals of the magnetic properties of spinel ferrites, including the interesting manifestation of noncollinear spin structures in YafetKittel triangular spin configurations. This is followed by description of some experimental observations on the structure and magnetic properties of (MnxAl1x)3O4 spinels and hausmannites, which exhibit YafetKittel-type ordering in their spin structures. I. Introduction

II.

Discussion: Structure, Magnetic Properties Relationships in Spinel Ferrites

magnetic properties of spinel-phase ferrimagnets are rich and complex. Ferrimagnetic couplings in systems with cations on A (or tetrahedral) and B (or octahedral) sites can involve exchange interactions between AA, AB, and BB as first proposed by Ne el.1 More exchange interactions are necessary to describe systems in which A or B (or both) are multivalent (or equivalently, if the constituent cations are distributed on both octahedral and tetrahedral sites). Further, in a variety of spinel systems atomic dipole moments need not be collinear; this results in so-called YafetKittel spin structures.2 In spinel-phase ferrimagnets disorder in the cation distribution between octahedral and tetrahedral sites can influence such fundamental magnetic properties as saturation magnetization, exchange couplings, and ferrimagnetic ordering temperatures.35 Technical magnetic properties such as dc, and ac permeabilities (associated with domain wall pinning) and hysteretic response also reflect disorder in the solid.612 Since magnetic properties are sensitive to structure, it has been suggested that magnetic properties may be used as a probe of disorder in ferrimagnetic spinels. However, given the complexity of the magnetic response, in order to make headway in using magnetic properties as a probe of atomic structure and disorder it is prudent to consider first the behavior of simple, model ferrimagnetic systems. Here, we review the fundamental, magnetic properties of spinel ferrites. This is followed by a description of some experimental observations on the structure and magnetic properties of (MnxAl1x)3O4 spinels and hausmannites (Mn3O4).1318
HE

(1) Structure of Spinel Ferrites Spinel-type magnetic oxides, which are exemplified by the spinel-structured ferrites (MFe2O4, where M is a divalent metal ion and Fe is a trivalent (ferric) iron ion), can be described by the formula AB2O4 where A and B refer to tetrahedral and octahedral cation sites, respectively. The oxygen anions are arranged in a face-centered cubic (fcc) lattice. Each unit cell contains 8 formula units with O2 anions in the 32(e) sites, and M3+ and M2+ cations occupying the 16(d) and 8(a) sites. The space group of ferrites is Fd3m and lattice parameters are typically 8.5 . Occupation of the tetrahedral (8a) site entirely with a divalent transition metal (such as Zn) produces a normal spinel structure, while occupation of the octahedral (16d) site with the divalent transition metal yields an inverse spinel structure. If divalent transition-metal ions are present on both A and B sublattices, the structure is mixed or disordered. In Fig. 1, the spinel structure is shown with the near neighbors for each of the cation sites marked. The relative positions of the A and B atoms to their near neighbor oxygen anions is quite important for strong superexchange, which is dependent on both the cationanioncation bond angle and the interatomic distance between the cations and anions. As discussed earlier, it is possible for the cation distribution to deviate from the normal spinel structure, in which case it is instructive to express the spinel formula by
2+ 3+ 2+ 3+ (M1 iFei )[Mi +Fe2i]O4

(1)

where the cations in parentheses are on A or tetrahedral sites and those in brackets are on B or octahedral sites. The parameter i represents the degree of inversion (i.e., fraction of Fe3+ on A sites).19 The extreme case of i 0 corresponds to the normal spinel structure; i 1 corresponds to the inverse spinel structure; and i 2/3 corresponds to a random distribution of cations. The equilibrium distribution of cations in the spinel structure depends on ionic radii, electronic configuration, electrostatic energies and polarization effects. Nonequilibrium cation distributions are possible using novel processing routes such as rapid solidification processing. The temperature dependence of cation disorder in spinels has been successfully modeled using a Boltzmann distribution: i1 + i
1 i2

= exp

Ei kB T

(2)

K. E. Sickafuscontributing editor

Manuscript No. 189658. Received December 28, 1998; approved October 14, 1999. Supported by the Air Force Office of Scientific Research, Air Force Materiel Command, U.S. Air Force, under Grant No. F49620-96-1-0454. *Member, American Ceramic Society. Present address: Innovative Materials Development Center, Japan Energy Corporation, Kitaibaraki, Ibaraki 319-15, Japan.

where Ei is the activation energy for interchanging an M2+ atom from a B to A site and returning an Fe3+ atom from the A to B site (these values are 0.110.14 eV for MgFe2O4 and CuFe2O4 ferrites).20 (2) Magnetic Moments in Spinel Ferrites In the crystal structure of ferrite (Fe3O4) (Fig. 1), we can imagine the unit cell as divided into eight octants for which
3342

December 1999

Magnetic Properties of Ordered and Disordered Spinel-Phase Ferrimagnets

3343

for which the net dipole moment per formula unit is obtained as follows: net/fu ( x)M + 10(1 x) (4)

This simple expression is observed to hold at x 0.2 for MnZn, CoZn, and NiZn ferrites, as seen in Fig. 2. The failure of such a simple model (as proposed in Eq. (4) by Ne el1) is due to limiting assumptions that do not allow for the natural fluctuations in the superexchange interaction due to compositional variations. Deviation from the simple linear dependence on x for x 0.2 requires a consideration of noncollinear spin structures (YafetKittel) arrangements, as described in the next section. Nonequilibrium distributions of cations in the spinel structure can also influence the intrinsic magnetic properties of these materials. This results primarily from valence state preferences of transition-metal species for different interstitial sites. For example, Mn2+ (moment 5 B) and Mn3+ (moment 4 B) prefer to occupy tetrahedral and octahedral sites in the spinel structure, respectively (in so-called 42 spinels it is possible to have Mn4+ ions with a 3 B moment).
Fig. 1. Spinel structure, indicating: (a) AA near-neighbors; (b) BB near-neighbors; (c) BA near-neighbors; and (d) AB near-neighbors (A sites black; B sites gray; oxygen white).

there are eight molecular Fe3O4 units. All oxygen atoms are tetrahedrally coordinated, while metal atoms occupy a fraction of the tetrahedral and octahedral interstices between oxygen ions. We can also substitute for the Fe2+ ferrous ion in magnetite to form the compound MOFe2O3, where M represents a divalent metal ion. The two variants, normal and inverse spinel, are distinguished by different occupations of the tetrahedral (A) and octahedral (B) sites, as summarized in Table I. To determine the specific magnetization of a given spinel ferrite we first consider Fe3O4 (FeOFe2O3). Each formula unit has two ferric (Fe3+) and one ferrous (Fe2+) ion. Hunds rules for the case of quenched (spin only) angular momentum (L 0, J S) reveals an atomic moment of 4 B for Fe2+ and 3 B for Fe3+. Given that Fe3O4 crystallizes in an inverse spinel structure (in which the Fe3+ on A sites couple antiferromagnetically with both the Fe2+ and Fe3+ on B sites), the net magnetic dipole moment per formula unit is 4 B. The magnetization (net dipole moment per unit volume) is given by the net dipole moment per formula unit multiplied by 8 formula units per cell and divided by the cell volume. In transition-metal-substituted ferrites with the inverse spinel structure, the antiferromagnetically coupled (A and B site) Fe3+ moments cancel. The net dipole moment per formula unit is then determined by the M2+ ion, as illustrated by the following examples: (a) MnOFe2O3 5 B; (b) FeOFe2O3 4 B; (c) CoOFe2O3 3 B; (d) NiOFe2O3 2 B; (e) CuOFe2O3 1 B; and (f) ZnOFe2O3 0 B. Actually, ZnOFe2O3 is known to possess a normal spinel structure in which half the Fe3+ on the B sites are oriented antiferromagnetically with the other half also yielding no net dipole moment. More complicated, ternary ferrites can also be considered. For example, in solid solutions of (MO,ZnO)Fe2O3, consideration of the site preference of Zn2+ ions for the tetrahedral A sites leads to the description of the ferrite as
2+ 3+ 2+ 3+ (Zn1 xFex )[Mx Fe2x]O4

(3) Exchange Coupling and Mean Field Theory in Simple Spinel Ferrites Magnetic ordering in spinels is described by mean field theory, which considers the exchange interactions between cations. Spinels are prototype ferrimagnets because of the common occurrence of different cation moments or of the same cation on different sites. In mean field theory, the magnetic ordering temperatures (either Curie or Ne el) are related to oxygen-mediated superexchange interaction between magnetic ions. Superexchange can be described in terms of electron hopping transitions between magnetic cations and oxygen anions. Consider an electron from an oxygen ion that is temporarily excited and transferred to an adjacent transition-metal ion. If the metal ion has a less than half-filled d-shell, then the transferred electron must possess the same spin as the electrons on the transition metal. This is in accordance with Hunds rule for high-spin metal ions, as are found in spinels. The Pauli exclusion principle requires the spin of the remaining unpaired electron on the oxygen atom to be of opposite spin compared with the electron transferred to the metal. With this, a negative exchange integral and antiferromagnetic coupling are anticipated,

(3)

Table I.

Site Occupancy in Normal and Inverse Spinels

Similar interstices (per unit cell) Number occupied (per unit cell) Normal spinel cation arrangement Inverse spinel cation arrangement

Site type

Tetrahedral (A) Octahedral (B)

64 32

8 16

8 M2+ 16 Fe3+

8 Fe3+ 8Fe3+ 8M2+

Fig. 2. Magnetic moments versus composition for various Znferrites, based on Eq. (4): straight lines Ne el model;1 curved lines YafetKittel model.2324

3344

Journal of the American Ceramic SocietyWillard et al.

Vol. 82, No. 12

according to the superexchange mechanism. Superexchange is dependent on the orientation of the p-orbital of the oxygen ion with respect to the near-neighbor transition metals. If the adjacent transition-metal ions are near 180 to an oxygen ion, the exchange integral will be large in magnitude and negative in sign (large antiferromagnetic coupling Jex << 0). However, as the angle is decreased to near 90, the exchange integral becomes small in magnitude and positive in sign (small ferromagnetic coupling Jex +0). The phenomenon of ferrimagnetism can be described further using Ne els two-sublattice theory. This model assigns two internal Weiss fields to the A and B sublattices, respectively.1 The sublattice magnetizations, MA and MB, are associated with moments of ions in the octahedral and tetrahedral sites. In Ne els two-sublattice theory, internal fields arise from AA, BB, and AB superexchange interactions. Originally, Ne el chose to ignore the AOA and BOB interactions (JAA and JBB) in his model for ferrites, considering only the AOB interactions (JAB). This seems acceptable from a superexchange argument since the angles of the AOB bonds are near 180 and the AOA and BOB bonds are closer to 90. By using a mean field approximation and a CurieWeiss model, Ne el was able to predict quite accurately the saturation magnetization of some of the inverse spinel ferrites, and their Ne el temperatures. Nevertheless, this model fails to describe the properties of mixed ferrite structures. Ferrimagnetic exchange can be complicated in three significant ways: (1) In the inverse spinel structure, the octahedral B sites are occupied by both divalent and trivalent ions which may have different moments. (2) The sublattice moments may, in fact, not be collinear. (3) Disorder may lead to different degrees of inversion for a given composition. Of these considerations, the first has been examined in the literature extensively.22 The second consideration is examined below. A more sophisticated model for exchange coupling in spinel ferrites was developed by Yafet and Kittel.2 They proposed subdividing the B cation lattice into B and B sublattices. For each formula unit, as stated earlier, there are two cations in octahedral sites and one cation in a tetrahedral site. To preserve fcc coordination when distinguishing B atoms using separate sublattices, we must consider the set of basis atoms associated with each Bravais lattice point. The basis consists of two formula units with four cations on octahedral sites (assigned labels B1, B2, B3, and B4) and two cations on tetrahedral sites (labeled A and A). Due to the positioning of the Bi sublattices with respect to the A sublattices, the B1 and B3 sublattices may be combined into a new sublattice, B. Similarly, the B2 and B4 sublattices may be combined to form a new sublattice, B. These combinations preserve the fcc symmetry and the symmetrical considerations for superexchange are unaltered. Now, AA, BB, BB, AB, AB, and BB exchange interactions must be considered. These, in turn, lead to the possibility of six distinct temperature dependencies for the saturation magnetization, M s ( T ) (associated with different temperature dependencies for the six exchange parameters). The interplay between competing exchange interactions for ions on common sublattices (A and A or B and B) allows for new, noncollinear magnetization behavior. This has proved especially important for mixed ferrites, where divalent transition metals are present on both sublattices. Figure 3 shows the temperature dependence of Ms for the six exchange parameters associated with the six possible exchange interactions. Four interactions (I, III, IV, and V) exhibit a single ferrimagnetic Curie temperature, while the remaining two interactions (II and VI) exhibit two ferrimagnetic Curie temperatures. In cases I, II, and IV, dMs/dT is not zero at T 0 K. This is in apparent contradiction with the third law of thermodynamics. However, the YafetKittel theory solves this dilemma by postulating noncollinear magnetization vectors MA, MB, and MB. These lead to so-called triangular spin structures. Hausmannite, Mn3O4, is an example of a YafetKittel spinel.21 Within the YafetKittel model, the mean field approxima-

Fig. 3. Saturation magnetization, M3, versus temperature. Transitions for six possible exchange interactions (based on the Ne el1 and YafetKittel2 models and denoted IVI) are shown.

tion is applied to each sublattice, based on the interactions from the neighboring sublattices and the other ions on the same sublattice. Next, the ground-state energy is derived from the interaction of the mean field with each sublattices dipole moments. The energy is minimized with respect to the angles between sublattices of the same type (A or B). This minimum energy allows for four different configurations of magnetizations. The configurations which are allowed consist of two antiferromagnetic arrangements (one intersublattice and one intrasublattice) and two triangular arrangements (one for canted moments on the A sublattices and one for canted moments on the B sublattices). Determination of the Curie points for each sublattice allows for additional configurations of the moments with changing temperature. The sublattice Curie temperatures are determined using the CurieWeiss law eigenvalues for the set of lattices. There are three possible Curie points: (1) the Curie point for sublattice A; (2) the one for sublattice B; (3) and Ne els result for the two-sublattice model. Upon examining the Curie points further, different transitions are found possible, depending on the order of the three Curie points. The simplifying assumptions for this model include the fol-

Fig. 4.

Equilibrium angles for the four sublattices.

December 1999

Magnetic Properties of Ordered and Disordered Spinel-Phase Ferrimagnets Table II.

Case Condition

3345

Summary of the Equilibrium Configurations for YafetKittel Ferrites

(rad) (rad) y

1 2 3 4

22 > 1 22 < 1 22 < 1 22 < 1

0 /2 /2 sin 1/(|2|y)

0 sin y/|2| /2 /2

All 0 < y < |2| |2| < y < 1/|2| 1/|2| < y

Fig. 5. (a) Mn2O3Al2O3 phase diagram, showing the spinel-phase field and the range of compositions from which it is possible to retain the spinel phase.14 (b) Mn3O4Al2O3 phase diagram. In (a) and (b), L liquid, H hausmannite (Mn3O4), B bixbyite (Mn2O3), C corundum (Al2O3), S spinel. Lowercase symbols indicate phases observed at room temperature.13,26

lowing: (1) magnetic moments on all of the sublattices are coplanar; and (2) magnetic moments of the ions on A and A are the same (as are the magnetic moments on the B and B sublattices). For this case, the energy is found to be E n Mb 2[(1 2 cos 2)y2 + (1 2 cos 2) + 4y sin sin ] (5) where i and i are molecular field coefficients, and y is the ratio of trivalent atoms on A lattice to B lattice. Angles and are defined with reference to Fig. 4. Four possible configurations of the equilibrium angles are found for the minimum in this energy, as summarized in Table II. The first configuration is that of antiferromagnetic coupling of A with A, and B with B. This is the case of the exchange parameter for similar sublattices (e.g., AA or BB) being much greater in magnitude than the exchange parameter corresponding to opposing sublattices (e.g., AB, AB, etc.). The second and fourth cases are similar, being triangular configurations of the moments, but on the B lattices and A lattices, respectively. Consider the second case (a similar argument will hold true for the fourth case), where /2 and the moments on the A and A sublattices are parallel to each other. The moments on the B and B sublattices are canted with respect to each other due to the BB exchange interaction being about the same as the AB (or AB) interaction. Since exchange interactions are negative, there is a competition between the JAB exchange and the JAA or JBB interactions. If the JBB exchange interactions are strong enough, the moments on the B sublattices can rotate away from a purely antiferromagnetic configuration with the A sublattices. This is a case that the simple Ne el model does not account for. The third configuration is the ferrimagnetic case, where mo-

ments on the A and A sublattices are parallel to each other and moments on the B and B sublattices are parallel to each other, but moments on A are antiparallel to those on B. This is the case of collinear moments that we generally associate with the Ne el model. The YafetKittel model description of canted moments can be used to describe magnetic moments in the Zn-ferrite system with x 0.2.2325 As described earlier, with increasing Zn content, the Ne el model predicts a linear increase in magnetization (Eq. (4)). But in the YafetKittel description, this linear behavior does not continue beyond x 0.2. This is because the exchange integral, JAB, decreases due to the dilution of the A lattice with increasing Zn replacement. As the Zn replacement reaches 0.2, the exchange integral JBB is approximately the same as JAB and the moments are no longer perfectly aligned. The canting of the moments reduces the net magnetization, as illustrated in Fig. 4. III. A Case Study: Manganese Aluminate Ferrimagnets As discussed above, cation disorder can influence such fundamental properties as saturation magnetization, exchange couplings, and magnetic ordering temperatures. We have initiated studies on a simple model system, manganese aluminate spinels, in order to study the effects of cation disorder on magnetic properties. The degree of disorder is influenced by the quench rate from a spinel-phase field (Fig. 5). The limits of metastability of the spinel phase (at room temperature) can be determined by a standard T0 construction. Manganese aluminate spinels (MnxAl1x)3O4 and the end-member hausmannite (Mn3O4) possess only one magnetic species, Mn (which can exist in more than one valence state). This system offers simplicity in the reduced number of exchange parameters required

3346

Journal of the American Ceramic SocietyWillard et al.

Vol. 82, No. 12

Fig. 6. (a) Typical magnetic hysteresis curves and their composition dependence for (MnxAl1x)3O4 spinels and hausmannites. (b) Composition dependence of the effective dipole moment per formula unit (at 5 T). (c) Composition dependence of the ferrimagnetic Curie temperature (same samples as in (b)).25

to describe interactions between magnetic ions. However, magnetic properties of manganese aluminate spinels are, in fact, richer than in other spinels, due to noncollinear spin arrangements (as observed in Mn3O4).21 We have synthesized (MnxAl1x)3O4 spinels with compositions varying from x 0.33 and x 1.0, by sintering mixtures of MnO and Al2O3 at temperatures of 1473, 1623, and 1823 K, followed by air- or water-cooling, to quench in the hightemperature spinel phase. X-ray powder diffraction revealed a single spinel phase for the composition range 0.42 < x < 0.67. Samples with x 0.33 and x 0.75 contained the spinel phase and a nonmagnetic corundum second phase. Samples in the composition range 0.85 < x < 1.0 exhibited a single hausmannite phase which is structurally related to the spinel phase. The magnetic properties of these materials have been investigated using SQUID magnetometry. This is discussed in more detail in Ref. 26. As shown in Fig. 6(a), magnetic hysteresis curves are, in general, nonsaturating to 5 T, which is consistent with the large energy barrier to rotating magnetic moments out of a triangular YafetKittel arrangement. In Fig. 6, the effective magnetic dipole moment is shown to increase monotonically with increasing Mn content (Fig. 6(b)) as is the Curie temperature, Tc (Fig. 6(c)) (though a slight Tc depression is observed for samples containing the distorted hausmannite phase). At present we have not attempted to construct a mean field theory to further elucidate these results. We believe it will be important to probe the very high field magnetic response as well as the Mn site occupancy, to improve our understanding of this interesting system. IV. Conclusions

The magnetic properties of spinel phase ferrimagnets are rich and complex. In a variety of spinel systems, atomic dipole moments need not be collinear; such spinels exhibit so-called YafetKittel spin structures. In spinel-phase ferrimagnets, disorder in the cation distribution between octahedral and tetrahedral sites can influence such fundamental magnetic properties as saturation magnetization, exchange couplings, and ferrimagnetic ordering temperatures. The magnetic properties of (MnxAl1x)3O4 spinels and hausmannites exemplify the complex behavior associated with spin structures and cation arrangements in YafetKittel-type spinels. References
1 L. Ne el, Magnetic Properties of Ferrites: Ferrimagnetism and Antiferromagnetism, Ann. Phys., 3, 13765 (1948).

2 Y. Yafet and C. Kittel, Antiferromagnetic Arrangements in Ferrites, Phys. Rev., 87 [2] 29094 (1952). 3 M. R. DeGuire; Ph.D Thesis. Materials Science and Engineering Department, Massachusetts Institute of Technology, Cambridge, MA, 1987. 4 M. R. DeGuire, R. C. OHandley, and G. Kalonji, The Cooling Rate Dependence of Cation Distributions in CoFe2O4, J. Appl. Phys., 65 [8] 316772 (1989). 5 M. R. DeGuire, G. Kalonji, and R. C. OHandley, Cation Distributions in Rapidly Solidified Cobalt Ferrite, J. Am. Ceram. Soc., 73 [10] 3202206 (1990). 6 M. Guillot, Material Science and Technology: A Comprehensive Treatment, Vol. 3B; Ch. 8. Edited by R. W. Cahn, P. Haasen, and E. J. Kramer, VCH, Weinheim, Germany, 1994. 7 D. J. Craik (Ed.), Magnetic Oxides, Wiley, London, U.K., 1975. 8 C. W. Chen, Magnetism and Metallurgy of Soft Magnetic Materials, North Holland, Amsterdam, Netherlands, 1977. 9 J. Smit and H. P. J. Wijn, Physical Properties of Ferrites, Adv. Electron. Electron Phys., 6, 69136 (1954); and Ferrites, Philips Technical Library, Eindhoven, Netherlands, 1959. 10 B. D. Cullity, Introduction to Magnetic Materials. Addison-Wesley, Reading, MA, 1972. 11 S. Chikazumi, Physics of Magnetism. Wiley, New York, 1964. 12 S. Greenwald, S. J. Pickart, and F. H. Grannis, Cation Distribution and g Factors of Certain Spinels Containing Ni++, Mn++, Co++, Al+++, Ga+++, and +++ Fe , J. Chem. Phys., 22, 1597600 (1954). 13 E. H. L. J. Dekker and G. D. Rieck, Revised Phase Diagram and X-ray Data of the Mn3O4Al2O3 System in Air, Z. Anorg. Allg. Chem., 415, 6980 (1975). 14 T. Ranganathan, B. E. MacKean, and A. Muan, The System Manganese OxideAlumina in Air, J. Am. Ceram. Soc., 45, 27981 (1962). 15 J. L. Snoek, Magnetic and Electrical Properties of the Binary Systems MOFe2O3, Physica (Amsterdam), 3 [6] 46383 (1936). 16 J. L. Snoek, New Developments in Ferromagnetic Materials. Elsevier, New York, 1947. 17 E. C. Snelling, Soft Ferrites: Properties and Applications, 2nd ed. Butterworths, London, U.K., 1988. 18 W. L. Roth, Magnetic Properties of Normal Spinels with Only AA Interactions, J. Phys. (Paris), 25, 50715 (1964). 19 E. J. W. Verwey and E. L. Heilmann, Physical Properties and Cation Arrangement of Oxides with Spinel Structures, Part I: Cation Arrangements in Spinels, J. Chem. Phys., 15, 17480 (1947). 20 E. F. Bertaut, Sur Quelques Progre ` s Rece nts Dans la Crystallographic des Spinelles, en Particulier des Ferrites (Recent Progress in the Crystallography of Spinels, in Particular the Ferrites), J. Phys. Rad., 12, 25255 (1951). 21 K. Dwight and N. Menyuk, Magnetic Properties of Mn3O4 and the Canted Spin Problem, Phys. Rev., 119, 147079 (1960). 22 J. B. Goodenough, Magnetism and the Chemical Bond. Wiley, New York, 1963. 23 E. W. Gorter, Magnetization in Ferrites: Saturation Magnetization of Ferrites with Spinel Structure, Nature (London), 165, 798800 (1950). 24 E. W. Gorter, Saturation Magnetization and Crystal Chemistry of Ferrimagnetic Oxides, Philips Res. Rep., 9, 295320 (1954). 25 N. S. Satya Murthy, N. G. Natera, S. I. Youseff, and R. J. Begum, YafetKittel Angles in ZincNickel Ferrites, Phys. Rev., 181, 96977 (1969). 26 Y. Nakamura, P. A. Smith, D. E. Laughlin, M. De Graef, and M. E. McHenry, Structure and Magnetic Properties of Quenched (MnxAl1x)3O4 Spinels and Hausmannites, IEEE Trans. Magn., 31, 415456 (1995).