IEEE TRANSACTIONS ON MAGNETICS, VOL. 47, NO.

12, DECEMBER 2011

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Advances in Magnetics
Hard Magnetic Materials: A Perspective
J. M. D. Coey
School of Physics and CRANN, Trinity College, Dublin, Ireland
The principles of operation of permanent magnets are summarized, and their development is reviewed. The key gure of merit, the energy product, improved exponentially over much of the 20th century, doubling roughly every 12 years. Yet it has not improved signif2 icantly in the last 20 years. Constraints on further development are explained, together with the limits of 1/4 0 s on energy product and 2 1 0 s on coercivity, where 1 is the uniaxial anisotropy constant and s is the spontaneous magnetization. The challenge of making rare-earth free magnets with a large energy product is discussed, as well as nanocomposite megajoule magnets and the development of new magnetically hard thin-lms with perpendicular anisotropy which are potentially interesting for spin electronics or magnetic recording. Index TermsMagnetic anisotropy, magnetic lms, neodymium alloys, permanant magnets.

I. INTRODUCTION

DECISIVE event in the history of magnetism occurred in the Netherlands in 1951 [1]. Before that, inexpensive permanent magnets could only be made in awkward shapesneedles, bars, and horseshoes. Steel needles had been used for a thousand years, their fabrication being clearly described by Shen Kwa at the beginning of the second millennium [2]. Horseshoes were popularized by Daniel Bernouilli after 1743, [3] and bar magnets were manufactured commercially by Gowind Knight from 1744 [4]. Even Alnicos [5], the new magnets of the rst part of the 20th century whose development was begun in 1931 by T. Mishima, had to adopt the bar or horseshoe shapes which still feature, misleadingly, in elementary school science texts, and seem to be ineradicably associated with magnets in the public imagination. The horseshoe remains the icon of a magnet, both in popular literature and safety signage. The reason for these awkward shapes is the demagnetizing [6]. For a uniformly-magnetized ellipsoid with mageld netization (1)

is the demagnetizing factor, which depends on shape where is 1/3 for a and takes values between 0 and 1. For example, sphere, 0 for a long needle magnetized along its axis or a thin lm magnetized in-plane and 1 for a thin lm magnetized perpendicular to the plane. Other shapes can be approximated by ellipsoids. Magnetic moment, the fundamental magnetic quantity for a solid, is measured in A m and magnetization is ratio of magnetic moment to volume. Thus , like , is measured in A
Manuscript received May 19, 2011; accepted August 16, 2011. Date of publication September 01, 2011; date of current version November 23, 2011. Corresponding author: J. M. D. Coey (e-mail: jcoey@tcd.ie). Color versions of one or more of the gures in this paper are available online at http://ieeexplore.ieee.org. Digital Object Identier 10.1109/TMAG.2011.2166975

m . An hysteresis loop is shown in Fig. 1. If the loop is not broad enough to take a positive value in the second quadrant , the magnetization collapses into a multidomain where state. The intrinsic coercive eld is the internal eld at which the magnetization reduces to zero. A hard magnet is one whose for a hysteresis loop is broad, with a coercive eld roughly equiaxial shape, whereas a soft magnet is one where the . When the hysteresis loop is loop is very narrow and measured in a closed circuit, where there is no demagnetizing eld, hard materials have a coercivity in excess of 400 kA m , whereas soft materials have a coercivity of less that 10 kA m . Materials with intermediate values are classied as semihard, and are mainly useful as magnetic recording media. The breakthrough that occured at Philips in 1951 was the discovery of a new family of materials, the ferrimagnetic hexagonal ferrites, which could be manufactured into magnets whose exceeded their spontaneous magnetization . coercivity This meant that the shape barrier was broken. Permanent magnets could henceforth be made in any desired shape, lifting an age-old constraint and giving free rein to the imagination of magnetic circuit designers1 . Nowadays, about one million tons of SrFe O and related hexagonal ferrites are produced every year. This averages out at about 140 g for everyone on Earth. The uses of ferrite magnets have multiplied, and we all benet from the availability of these cheap permanent sources of magnetic eld. Although thin lms with perpendicular anisotropy are useful for spin electronics and magnetic recording, it is pointless to , because a uniform permake a permanent magnet with pendicularly-magnetized lm will generate no stray eld. This point is demonstrated in Fig. 2. The stray eld is the -eld created by a magnet outside its own volume, whereas the demagnetizing eld is the -eld created within its volume. The reason we need permanent magnets is to produce a stray eld
1A material which could retain its magnetization in any shape, CoPt, had been discovered earlier, but prohibitive cost restricted its application to a few military purposes.

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Fig. 1. (a) An ( ) hysteresis loop for a hard magnetic material, with indications of the crystallite structure and domain structure at different points around the loop. The dotted line, with slope 1 , intersects the loop in the second quadrant at the working point of the magnet. (b) An ideal hysteresis loop, where the magnetization remains fully saturated until it reverses in the second quadrant. The coercivity should exceed half the magnetization if the maximum possible energy product is to be achieved. Note that is the eld acting in the magnet, which differs from the applied eld by the demagnetizing eld; = + . is the shaded area. The corresponding ( ) loop is indicated by the dotted line;

MH

0 =N

BH

jBH j

H H H

loop of the magnet itself. The loop is deduced the loop via the dening equation from the (2)
Fig. 2. Demonstration that a uniformly-magnetized lm produces no stray and . The eld: The magnetization is resolved into components = 0, hence = 0. Since the parallel in-plane demagnetizing factor component of is continuous at the interface, there is no stray eld produced . For the perpendicular component the demagnetizing factor, = 1, by and = . It follows from (2) that = 0 inside the magnet. Since the perpendicular component of is continuous at the interface, it is zero outside the magnet as well, and no stray eld is produced by either.

M H

H 0M

M
N

We distinguish between for the hysteresis loop of a real magnet [Fig. 1(a)], and , the absolute upper limit which is deduced for an ideal square loop [Fig. 1(b)]. For any magnetic circuit made of ferromagnetic material with magnetization , the magnitude of the stray eld at any point in space scales with (3) The energy density in a magnetic eld is , so the en. The best we can hope to ergy product is proportional to loop of Fig. 1(b) where the magneachieve is the ideal tization remains fully saturated well into the second quadrant. Then

outside their volume in a region known as the air gap, with no continual expenditure of energy. A uniformly-magnetized lm or platelet is useless in this respect. The customary gure of merit for a permament magnet is . This quantity is twice the energy its energy product stored in the stray eld created by the magnet, and it is related to

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TABLE I PROPERTIES OF SINTERED AND BONDED FERRITE MAGNETS

Fig. 3. Optimum shapes for permanent magnets (a) pre 1950 and (b) post 1951.

Finding the maximum by differentiating with respect to and

gives (4)

An approximation to a shape with is a cylinder whose height is equal to its radius. This is the new icon of permanent magnetism (Fig. 3), although it lacks the brand recognition of the horseshoe. Unfortunately the hexagonal ferrites, being ferrimagnetic materials with two opposing magnetic sublattices and largely composed of nonmagnetic oxygen ions, do not have much magnetifor BaFe O or SrFe O , zation. At room temperature is 380 kA m , less than that of nickel and about a fth of that of iron. It is worth emphasizing that many permanent magnet applications depend on the square of the magnetic ux denassociated with the stray eld produced by the sity magnet in an air gap. This scales with the magnetization of the magnet itself, (3). This idea is captured in the use of energy product as the gure of merit. Implicit in the discussion so far is the assumption that the permanent magnet has an easy axis of magnetization. The magnetization lies in one or other direction along the easy axis, and switches at the coercive eld. The principal origin of this anisotropy is magnetocrystalline, and it is linked to spin-orbit coupling. Requirements for uniaxial anisotropy are that the magnet should have a uniaxial crystal structuretetragonal, rhombohedral, hexagonalwith a positive anisotropy constant , where the anisotropy energy is written as an expansion whose leading term is (5) where is the angle between the magnetization direction and the easy axis. Further terms in the expansion reect the crystal symmetry, but for many purposes it is enough to consider only the leading term. The criterion that a magnet can be fabricated in any shape without demagnetizing itself may be formulated in terms of the magnetic hardness parameter of the material dened as [7] (6) The minimum requirement for an optimized permanent magnet is that . The physical limit on coerwith civity is the anisotropy eld (7) which is the value found for coherent rotation of the uniform magnetization of a single domain particle in the Stoner-Wohlfarth model. The coercivity for any other reversal mechanism is

smaller [8]. Hence the bare minimum requirement is . In fact, experience shows that the best coercivity that can be achieved in a practical magnet rarely exceeds 20%30% of the anisotropy eld associated with the magnetocrystalline needs to be about four times greater anisotropy [9], so that than would be expected from the Stoner-Wohlfarth model. A . more realistic criterion for a hard magnet is therefore It is rather easy to nd hard magnetic properties in materials which have little magnetization. A nice example of a weaklymagnetic, hard material is hematite, Fe O . It is a canted antikA m , and at room temperaferromagnet with is ture is 9 kJ m [6]. The magnetic hardness parameter huge, so there is little difculty in obtaining hysteresis loops that show coercivity greater than the magnetization, but hematite magnets produce so little stray eld as to be practically useless. Coercivity becomes increasingly elusive as the magnetization increases. For hard magnets with sufcient magnetization should be at least 250 kJ m . to produce a useful stray eld, kJ m and . The hexagonal ferrites have These hard ferrites are ceramics, usually composed of crystallites that are platelets a few microns in diameter. They, and other magnets, are frequently sintered into dense masses, with or without prior orientation of the grains. Alternatively, the ferrite may be mixed with a polymer to make a moldable bonded magnet where up to 70% of the volume is occupied by the ferrite grains, which may or may not be oriented. Density and degree of orientation are critical process variables for improving energy product. The point is illustrated in Table I. A fully-dense and perfectly oriented hexagonal ferrite would have a hypothetkJ m . If the grains are ical energy product oriented at random, but are magnetized along the easy direction with the direction of overall which makes an angle magnetization, the magnetization is reduced to . The energy product is therefore reduced by a factor of 4. If the grains in a polymer composite are oriented, the magne, and the energy product is about a tization is reduced to factor of two less than the ideally dense case. Worst of all is the isotropic bonded magnet, with an energy product less than 1/8 of the ideal. The cost of the material and processing steps must be weighed against the stray eld requirement for any particular application. II. PERMANENT MAGNET MATERIALS Even after the arrival of ferrite magnets, the use of alnico , because they had magnets continued, despite their (up to 1.1 MA m ), higher Curie temperature a larger

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( K), and a greater energy product (up to 70 kJ m ). Alnicos are nanostructured two-phase magnets, developed in the earlier part of the 20th century, where CoFe needles with are embedded in a NiAl matrix. The anisotropy constant in (5) is esssentially due to shape anisotropy, for which the expression is [6] (8) , with the maximum Hence it follows from (6) that . For CoFe, can be as high value occuring when as 1.2 MJ m , but alnico magnets nonetheless needed to be cast in the form of bars or horseshoes. Shape anisotropy is never enough. The landscape was transformed by the advent of the rst rare-earth permanent magnets in 1966 [10]. SmCo is an intermetallic with the hexagonal CaCu structure which exhibits MJ m , and truly enormous uniaxial anisotropy, kA m , which is much greater than that of ferrite. It was relatively easy to fabricate magnets from this material , since . Energy products of up to 190 with kJ m , were achieved. The quest for ever-higher energy products led to the emergence of magnets based on the related compound Sm Co which crystallizes in the hexagonal Th Ni or rhombohedral Th Zn structures, which give much less anisotropy but a higher magnetization. The development of coercivity in the new structure was the outcome of an extended period of optimization of the microstructure by modifying heat treatment, stoichoimetry, and composition. The 2:17 magnets continued to deliver increasing energy products throughout the 1970s. Optimized magnets, denoted as Sm(Co, Fe, Cu Zr) , have MJ m MA m and . Energy products rose to 260 kJ m . But there was a drawback. Widespread adoption of Sm-Co magnets was impeded by their cost. The base metals were expensive, and the cobalt supply was erratic and insecure. At that time, cobalt came mainly from Zaire and the supply was inuenced by the political chaos in central Africa. Alternative sources were subsequently found, but cobalt is inevitably expensive because its abundance in the Earths crust is 2000 times less than that of iron, as shown in Fig. 4. In fact iron in about forty times as abundant as all the other magnetic elements put together. Besides being cheap, it is the ferromagnetic element with the largest magnetization at room temperature, MA m . Irons cubic structure precludes the development of significant coercivityenergy products of steel magnets were only a few kJ m but if an iron-rich uniaxial compound could be found, it would mean a breakthrough in permanent magnetism. And found it was. The guiding principle was to look for an intermetallic like SmCo or Sm Co , which combined iron with a rare earth in a uniaxial crystal structure. The role of the rare earth is to produce much of the uniaxial anisotropy, while contributing to the ferromagnetic moment of the compound. Regrettably. the 1:5 structure does not form with iron. Table II shows the hypothetical contribution to the magnetization of an atom element based on ferromagnetic alignment of the of a 3d or zero-temperature atomic moments.

Fig. 4. Crustal abundances of some magnetic elements.

Exchange between 3d and atoms involves their spin. The 3d atoms can be regarded as spin-only atoms, but Hunds rules apply to the rare earths so that the spin and orbital moments are oppositely directed for the light rare earths, but they are parallel spin mofor the heavy rare earths. Moreover, the small ment which mediates the exchange means that their magnetic behavior is like that of a light d element [11]. Light and heavy d elements couple with their spins opposite. The hierachy of interactions in rare-earth intermetallics is . Unfortunately, manganese, with its large moment and almost half-lled d band tends to be antiferromagnetic. The spins of iron, cobalt and nickel, where the 3d band is much more than half full, couple antiparallel to the rare-earth spin, which leads to parallel coupling of the 3d and moments for the light rare earths, but antiparallel alignment for the heavy ones. Data on numerous rare-earth intermetallics bear this out [12]. The most favorable combination is therefore . Unfortunately, there are no suitable Nd-Fe compounds in the binary phase diagram. So the challenge was to come up with a stable ternary with the least possible amount of a third element, to minimize dilution of the magnetization. The fortuitous discovery of just such a ternary phase was announced by two groups, working independently, in 1982 [13], [14]. Croat and co-workers used melt spinning to produce a nanocrystalline coercive Nd-Fe-B alloy which became known by its trade name as MAGNEQUENCH, while Sagawa and co-workers found the hard magnetic compound by more traditional methods of intermetallic synthesis, and named it NEOMAX. The ternary tetragonal phase, Nd Fe B was what the world had been waiting for. It was intensively studied during the 1980s and 1990s [15], not least in Europe by the participants in the Concerted European Action on Magnets [16]. The magnetization was 1.28 MA m and was 1.54. The long process of microstructure optimization led to further doubling of the energy product, up to its current record value of 474 kJ m for a laboratory magnet [17]. It turned out that the ternary Nd-Fe-B phase had actually been syntheized as far back as 1979 by Kuzma and coworkers [18], but no magnetic characterization was done. Modern information technologywhich owes much to Nd Fe B magnetswill probably ensure that no similar oversight occurs in future. Furthermore, high coercivity and energy product for a melt-spun and annealed Fe Pr B Si alloy had been reported

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TABLE II POSSIBLE CONTRIBUTIONS TO THE MAGNETIZATION FROM DIFFERENT ELEMENTS. THE RARE EARTHS ARE ASSUMED TO HAVE A TRIVALENT 4f CONFIGURATION. THOSE IN BOLD TYPE HAVE A FERROMAGNETIC GROUND STATE. THE SIGN OF THE ATOMIC QUADRUPOLE MOMENT Q IS ALSO SHOWN

in 1983 by Hadjipanayis et al. [19], which may have been the rst observation of the magnetic signature of a 2-14-1 phase. Case histories of this and other intermetallics and strategies for identifying new ones were reviewed by Stadelmaier [20] The new material soon established itself as the leading high-performance magnet, and it facilitated the small spindle motors and voice coil actuators that were needed for thin hard-disk drives, thereby enabling the realization of laptop computers and compact servers. Nd Fe B is an almost ideal hard magnetic materiallargely composed of iron, which is very cheap and has a large ferromagnetic moment, with a relatively small amount of an abundant light rare earth to boost the magnetization and provide much of the anisotropy, in a tetragonal crystal structure stabilized by the boron atoms which occupy just 2% of the volume of the unit cell. Who could ask for anything better? One point regarding alloy design needs to be elaboratedthe sign of the unixial anisotropy constant in (2). This depends on at the rare earth site the product of the electric eld gradient which is governed by the crystal structure, and the sign of the shell, quadrupole moment Q of the unpaired electrons in the which follows the quarter shell rule, as indicated by the signs in Table II. Similar considerations apply for the 3d atoms. This means that a structure that is easy-axis for Co will be easy-plane for Fe and vice versa, and that a site which is easy-axis for Sm is easy-plane for Nd and vice versa. In the Nd Fe B structure, both the Nd and Fe sublattices contribute to the uniaxial easy MJ m and MJ m . anisotropy, with Likewise, in the CaCu structure, both the Sm and Co sublatMJ m tices make positive contributions, with and MJ m . In fact Nd Fe B has two weaknesses: a) the rather low Curie temperature of 588 K and . b) the relatively small value of As a result, the unalloyed material does not have good high temperature performance. Both can be remedied, at a price, by suitable substitution: the Curie temperature can be increased by cobalt substitution. Cobalt has the highest Curie temperature of any material, 1360 K, compared to 1044 K for iron, but it is expensive and it reduces the anisotropy in the tetragonal 2:14:1 structure. The anisotropy can be best increased by terbium or slightly, but dysprosium substitution, which also increases

at the expense of reducing the magnetization because a heavy rare earth couples antiferromagnetically with iron. The uniaxial anisotrtopy of Tb is a little greater than that of Dy, and its moment is smaller [6]. Nevertheless, Dy is more commonly used as an additive because it is about half the price of Tb. No better magnet than Nd Fe B has been discovered since. The optimization of the material has proceeded to the point , are very close to , where the best values of for the phase, 512 kJ m . The exponential improvement in energy product over most of the 20th century illustrated in Fig. 5 led to nave expectations by the uninformed that the progress would continue unabated. The pressure to develop better magnets was commercial, to enable new products like laptop computers which would not have been possible without high-grade Nd-Fe-B magnets. Yet the energy product has not doubled in 20 years, and it is unlikely to do so ever again. One interesting new development in the 1990s was the use of interstitial modication to tune the crystal eld, and increase the Curie temperature of iron-based intermetallics [21]. The process was discovered for Sm Fe , an iron-rich intermetallic with an unimpressive Curie temperature of 389 K and easy-plane anisotropy. The properties are transformed by the introduction of three nitrogen atoms which occupy a triangle of interstitial sites around the rare earth. They increase by 360 K, but they the unit cell volume by 6%, which raises also produce a strong negative electric eld gradient at the rare to 8.6 MJ m . earth site, increasing The drawback of Sm Fe N is that it cannot be sintered into fully-dense oriented magnets, because the nitrogen is driven off at high temperature. The material is suitable for niche applications in oriented polymer-bonded magnets. Interstitial modication with C or N has also been applied to iron-based alloys with the ThMn structure. A summary of the intrinsic properties of rare-earth and other permanent magnets is given in Table III. Some conversions to the often-used cgs units are given at the bottom of the table. The magnetic properties, processing, and applications of rare-earth iron permanent magnets have been summarized in a multi-author monograph [22]. Some of the latest applications are discussed in a recent review [23]. The world market for permanent magnets is now split roughly evenly between Nd-Fe-B and hexagonal ferrite, with smaller amounts of Sm-Co, alnico, and other materials.

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Fig. 5. Progress of energy product in the course of the 20th century. TABLE III INTRINSIC MAGNETIC PROPERTIES OF SOME PERMANENT MAGNET MATERIALS [6].

III. WHERE ARE THE LIMITS? Exponential improvements in technology must come to an end, either because of an immovable physical constraint on further growth, or else because further improvements become pointless. An example of the latter is the permability of soft magnetic material, where values are available which are adequate for any known application. Hard magnets and hard-disk recording are examples of the former. The primary limit on energy product is the saturation magnetization, (4). The greatest magnetization to be found in a bulk ferromagnet at room temperature is in the bcc Fe-Co alloy MA m . If this known as permendur, which has MJ m ) was a uniaxial hard magnet with kJ m , we could instead of a soft cubic alloy with to 1190 kJ m , over twice its present value. raise The Slater-Pauling curve is a famous plot of the average moment in Bohr magnetons per atom versus the average number of 3d electrons in a series of binary alloys. When the 3d band , which means that the is nearly full, the slope of the plot is

-band is completely full, and the changing number of elec-band. Such altrons is reected in the population of the loys are known as strong ferromagnets. Nickel and cobalt are strong ferromagnets, with moments of roughly 0.6 and 1.6 per atom. The Fe Co composition is at the limit of strong ferromagnetism. Iron itself is a weak ferromagnet, with a moper atom and there are holes in both ment of 2.2, not 2.6 and -bands. One way to increase the moment might be to make the bands narrower to maintain a full band, which could be achieved by somehow expanding the lattice to reduce the transfer integrals that determine the bandwidth. But this is self-defeating because what we are looking for is an increase in , not the moment per atom. Expanding the lattice reduces . Despite claims advanced for thin lms of Fe N [24], we have no bulk ferromagnetic material with a magnetization at room temperature that surpasses that of Fe Co . The other hard limit is that set on coercivity by the anisotropy eld, (7). A bulk ferromagnet in the permanently-magnetized state is metastable; the ground state would be a multidomain state that generates no stray eld. A perfect single crystal readily

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Fig. 6. Progress in coercivity during the 20th century, showing the upper and lower extremes [6].

adopts this equilibrium magnetic conguration, and shows no coercivity. In order to stabilize a metastable state with well into the second quadrant of the hysteresis loop, it is necessary to engineer a microstructure that discourages nucleation of reverse domains and impedes the propagation of domain walls. There is no magic recipe for this; optimization of the microstructure of a new permanent magnet to yield useful coercivity and a nice square loop is a long drawn-out empirical process lasting many years, which is all the more difcult when is not much greater than 1. The anisotropy eld is equal to the coercivity of a tiny, uniformly-magnetized Stoner-Wohlfarth particle where magnetization reversal proceeds by coherent rotation. Very large coercivities have been achieved thin lms composed of single-domain particles; in a layer of isolated FePt nanoparticles, for example, exhibited a coercivity exceeding 90% of the anisotropy eld [25]. But in any real bulk material, there are always defects and magnetization reversal takes place by a nonuniform process of nucleation and propagation of reverse domains, which occurs more readily than coherent rotation. The strategy for optimization of the microstructure is to avoid nucleation sites, and pin reaches the domain walls at thin planar defects. Typically, % of after a lengthy optimization process. It is no exaggeration to say that the entire progress in magnetic materials in the 20th century lies in the mastery of coercivity, Fig. 6. This has been a largely-empirical process, aided by a physical understanding of reversal mechanisms and high-resolution electron microscopy. The third constraint on permanent magnet performance is the Curie temperature. We still know of no higher Curie temperature for most ferromagnets is than that of cobalt (1360 K), and much less. To avoid unwelcome changes in magnet performance to C, which is often speciin the temperature range ed for a material operating at ambient temperature, a minimum Curie temperature of 500 K is needed. Some applications, in aircraft engines for example, require magnets to run at much higher in an iron-based temperatures. The main strategy for raising alloy is to substitute cobalt for iron. Finally there is the issue of raw materials and processing costs. This is barely a constraint for thin lm devices with hard magnetic layers. To provide a chip for everyone on Earth which

includes a thin lm a couple of nanometers thick requires only about ten moles of material. One is free to choose practically any stable element from the periodic table if it is really needed to do the job. The situation is completely different for bulk magnets, where each magnet can include an appreciable fraction of a mole of raw material (a mole of most elements is approximately 10 cm ), so a billion moles may be needed to make one for everyone on Earth. For mass markets, the raw materials need to be cheap, or at least relatively inexpensive. Expensive materials, like Dy in Nd Fe B, may be included in small proportions as additives. It is possible to use expensive or very expensive materials as the basis of magnets destined for high-value niche applications in aerospace or the military. The US Navy, for example, used CoPt magnets at one time for microwave tubes. The cost of an element scales roughly inversely with its crustal abundance. The correlation is shown in Fig. 7, where a periodic table is included which assigns the elements into the ve cost categories. In comparison with other elements of ppm, rare earth production is low, comparable abundance, and prices are high. IV. NEW DIRECTIONS Interest in hard magnetic materials is now reviving [26], after a period when research in permanent magnetism had ebbed, The lull had been due to the failure of the community to come up with a better magnet than Nd Fe B. Most efforts in recent years, notably in Japan, have been devoted to incremental improvement of the Nd-Fe-B magnets by rening the grain boundary microstructure with the help of advanced microscopic techniques so as to enhance the coercivity and energy product. As a result, the material now has the temperature stability needed for use in electric vehicles [22]. There has also been an effort to reduce or eliminate dysprosium or terbium additions, for strategic reasons [27]. Many monazite and bastnaesite ores rich in light rare earths are slightly radioactive, due to the presence of thorium. Most easily-exploitable ores are found in China, and the current sources of the heavy rare earths such as dysprosium and terbium are almost exclusively Chinese. We consider three challenges which may shape future research in hard magnetism.

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Fig. 7. (a) Correlation of crustal abundance of the elements, and their cost per mole. (b) Periodic table, classifying the elements into ve categoriesvery cheap (white), cheap (pale grey), moderately inexpensive (light grey), expensive (dark grey), and very expensive (black). Unstable elements are omitted.

A. The High-Performance Rare-Earth Free Magnet Nd-Fe-B has been caught out by its own success. Potential new applications in wind turbines and electric vehicles [23] may demand a multiple of the current annual production of about 80 000 tons. Although there are ample reserves of rare earths throughout the world, including recently-discovered reserves in deep-sea mud in the Pacic Ocean [28], current rare-earth oxide production and magnet manufacture is concentrated to a large degree in China, where national interests may clash with purely commercial considerations regarding the export of rare-earth oxide, metal, or nished magnets. It is unclear whether present sources of supply of rare earth metals from mines in China, which currently furnish about 95% of the total, will be willing or able to meet the demand. This is the current rare earth crisis [27], which mirrors the cobalt crisis of the late 1970s and early 1980s. Rare earth prices have doubled recently. The supply situation is particularly acute for the heavy rare earths, and especially for dysprosium or terbium, which is needed to deliver the temperature stability up to 200 C required for the motors in electric vehicles. Currently most of the worlds heavy rare earths comes from ytrium-rich ores in

South China. There is therefore pressure from funding agencies to come up with a high performance magnet which uses less heavy rare earth or, better still, little or no rare earth at all. What are the prospects? Suppose we want a magnetic material with kJ m and as a Nd-Fe-B substitute. According to (4), this means than the magnetization should exceed 1.26 MA should exceed 2 MJ m , acm . Furthermore, for cording to (6). Thirdly, the Curie temperature should be greater than about 550 K. Table IV provides a summary of properties of a few uniaxial ferromagnetic materials, which approach the requirements in some respect. It is possible to reach each target individually, but no material manages to score more than two out of three. The magnetization of the selection of materials in the table shows that the target value of 1.26 MA m may be achievable, provided not too much of the nonmagnetic partner element is present. The tetragonal L1 structure is potentially interesting, but if only half the atoms in the alternating layers is magnetic, as in carbon-stabilized MnAl, the magnetization will inevitably fall short of the target. Tetragonal MnAl is a permanent magnet is only 112 kJ m and the achievable material but

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TABLE IV PROPERTIES OF SOME UNIAXIAL FERROMAGNETS [6], [29], [30]

energy product is much less. Table IV also shows that substantial values of Curie temperature and uniaxial anisotropy can be achieved without rare earths in uniaxial crystal structures. Here the severe tetragonal distortion of the cubic Heusler structure -type Mn Ga is a good example, but unfortunately the in magnetic structure is ferrimagnetic, suffering from the tendency of manganese atoms to couple antiferromagnetically. The table shows that the target values for the three key properties can be achieved individually, and suggests that there is no reason in principal why we should not have them all. A material where they are achieved simultaneously may or may not exist, but it has yet to be discovered. The properties of many of the families of rare-earth free permanent magnets are summarized in the book by McCurrie [29] The contribution of the 3d sublattice in magnets like SmCo and Nd Fe B to the overall uniaxial anistropy can be seen from the data on the yttrium analogues in Table IV. The presence of a heavy nonmagnetic atom may help to enhance the spin-orbit coupling at the 3d site by hybridization, but other examples in the table show that it is not essential. There is little prospect of replacing rare earths by actinides. Other than depleted uranium, none are available in sufcient quantities, and uniaxial actinide intermetallics with high Curie temperatures have not yet been found. Nevertheless, huge anisotropy can be obtained, as the example of the sulphide US shows [6] While the likelihood of nding a rare-earth free replacement for the best Nd-Fe-B magnets is slim, there are better prospects of nding a new cheap magnet with better properties than hexagonal ferrite. An energy product of more than 100 kJ m should MA m MJ m ), with be within reach ( interesting engineering and economic consequences. B. The Megajoule Magnet An idea that has informed much of the recent research on hard magnets is the exchange spring, originally proposed by Kneller and Hawig [31]. The idea is that hard and soft phases can be exchange-coupled in an appropriate nanostructure in such a way that the composite as a whole exhibits hard magnetic properties. The concept was further developed by Skomski and Coey [32] who showed that the length scale of the soft phase should be on the order of the domain wall width of the hard phasea few nanometersand they suggested that it may be possible to achieve an energy product in excess of a megajoule per cubic meter in an optimized hard/soft nanocomposite. There has been progress in demonstrating the exchange spring concept experimentally in model systems, where energy for the hard phase have been products in excess of

achieved [33]. Efforts are ongoing to create composites of ultrane nanoparticles without oxidation or excessive grain growth. Diffuse interfaces between hard and soft phases have been found to improve the coercivity [34]. A selection of results is presented in Table V. Techniques used to produce the nanocomposites, recently reviewed by Liu [35], include melt spinning, bilayer or multilayer thin lm deposition, core-shell nanoparticle assembly, mechanical alloying, surfactant ball milling, warm compaction, explosive compression, and shear extrusion. Respectable energy products of order 160 kJ m have been achieved for isotropic bulk material, with relatively little rare earth. The energy product of the nanocomposite may be as much as three times that of the isotropic hard phase [41]. Some degree of anisotropy of the soft phase helps to improve the magnets. However, it will be necessary to achieve a considerable degree of orientation of the hard nanocrystallites if progress is to be made . If competitive bulk magnets in advancing the record are ever to be produced using this approach, it will be necessary to devise a cost-effective manufacturing procedure for creating a thermally-stable, oriented nanostructure, perhaps analagous to the procedure used to create oriented alnico, but on an even smaller scale. Die upset forging shows promise [35], but this is a big challenge. Let us suppose for a moment that the hard nanoparticles can be fully aligned, and assume that volume averaging of the properties of the hard and soft phases can be achieved. Is it possible to produce a magnet with an energy product of 1 MJ m , based on the hard and soft materials known at present? From (4), the average magnetization must be at least MA m , and the averaged anisotropy from (6) should MJ m . As the soft component, we should be choose the Co-Fe composition with the maximum magnetization 1.95 MA m . If it is combined with SmCo , which has MA m , then 15% of the volume is available for the hard phase. Since the anisotropy of SmCo is 17.2 MJ m , the average anisotropy is 2.5 MJ m . Alternatively we could MA m and try Nd Fe B, which has MJ m as the hard phase. The available volume is then 24%, but the averge anisotropy is 1.1 MJ m . Of course, anisotropy can be increased by terbium or dysprosium substitution, but this reduces the magnetization of the hard phase, and hence the percentage of the volume that can be allowed for it. Sm Fe N is a slightly better prospect, but the averaged anisotropy is only 1.9 MJ m The original proposal for a megajoule magnet [32] was an upper limit based on the most favorable case, where the coercivity is and it is equal to the anisotropy eld .

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TABLE V SOME RESULTS ON HARD/SOFT NANOCOMPOSITE MAGNETS

The criterion that can be relaxed if it is possible to increase the coercivity beyond about a quarter of the anisotropy eld. There is some precedent for this in model systems, but it seems that the megajoule magnet will remain elusive. C. Thin Films With Perpendicular Anisotropy Thin lms generate no stray eld when uniformly magnetized (Fig. 3). Magnetic media are written with regions of alternating magnetization in tracks in continuous media, or in individual isolated nanodots in bit-patterned media. In this way they generate a characteristic pattern of stray eld, which is read by the read head. Current media are continuous metal lms composed of tall nanoscale grains of CoPtCr, which exhibit perpendicular anisotropy [47]. The condition for perpendicular anisotropy is , or (8) , In terms of the hardness parameter, the condition is (5), requires inso increasing stray eld, which scales with . Future bit-patterned media are likely to be made creasing of thin lm hard magnetic materials with a relatively high magnetization, such as FePt, CoPt, or Mn Ga, patterned on a 10 nm scale [48]. Possible ways of producing these media include self-assembly, the use of block copolymer masks [49], electron beam, and nanoimprint lithography. Materials previously considered for permanent magnets are now being considered for magnetic media. A novel problem is that materials which exhibit enough anisotropy for the magnetization to be stable at very small volumes according to the condition (9) are single-domain particles where the coercivity is a signicant fraction of the anisotropy eld. The coercivity has to be MA m for the medium to be able to be written in the stray eld of the write head. Various approaches including heat- or

microwave-assisted recording and graded media are being explored [50]. A different application of perpendicular lms is magnetic memory. Here there is no need to produce a stray eld, and the lm is uniformly magnetized. The requirements are that the Fermi level spin polarization of the feromagnet should be as large as possible to facilitate spin-transfer torque in giant magnetoresistance or tunnel magnetoresistance spin valves, and that the Gilbert damping parameter should be as small as possible. Equation (9) must be satised for long-term stability of the information in sub-100 nm memory cells. Here there are good chances of nding new materials or multilayers which can be grown as smooth lms with suitable perpendicular anisotropy and spin polarization. V. CONCLUSION The prospects of nding a new bulk permanent magnet with better magnetic properties than Nd Fe B, and its derivatives, appear to be dim. However, it may well be possible to nd a new rare-earth-free magnet where the anisotropy is derived from the 3d atoms in a uniaxial structure. There is a need for a systematic study of possible structure types, including electronic structure calculations to help with exploratory alloy design. A target of 200 kJ m , which is about ve times the best that has been achieved with these materials so far, would be ambitious, but the role of serendipity should never be discounted. The exchange-spring approach in two-phase nanostructures depends on orientation of the hard phase to achieve a new record energy product, but this will be very challenging unless some process for nanoscale demixing can be found, analagous to that used for alnico. While there is some prospect of increasing the , the megajoule magnet seems to be just out value of of reach. A relatively unexplored area, where prospects of success are higher, is the development of new hard magnetic lms with perpendicular anisotropy for applications in spin electronics and magnetic recording.

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