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JOURNAL OF IRON

AND STEEL RESEARCH,

INTERNATIONAL. 2007, 14(4) : 69-74

Nanocrystalline and Nanocomposite Magnetic Materials and Their Applications

Robert D Shull
(Magnetic Materials Group, National Institute of Standards and Technology, Gaithersburg MD 20899, Maryland, USA)

Abstract: Nanocrystalline materials can possess bulk properties quite different from those commonly associated with conventional largegrained materials. Nanocomposites , a subset of nanocrystalline materials, in addition have been found to possess magnetic properties which are similar t o , but different from, the properties of the individual constituents. New magnetic phenomena, unusual property combinations, and both enhanced and diminished magnetic property values are just some of the changes observed in magnetic nanocomposites from conventional magnetic materials. Here, a description will be presented of some of the exciting new properties discovered in nanomaterials and the magnetic applications envisioned for them. Key words: nanocomposite; ferromagnet ; magnetoresistance; magnetic refrigeration; domain imaging

There are three basic reasons why one might expect to see changes in properties of materials as some material dimension is reduced to the nanometer level. (1) Quantum confinement, where the energy levels of the atom, electron, o r nucleus change as the size of the confined region changes; the wellknown particle in a box situation. Since the quantized energy levels (En) vary inversely with the size of the box ( L ), small changes in L when that size is small amount to very large changes in the energy levels. Small changes in L when L is large do not result in large shifts in the energy levels. Therefore any property which depends on the value of the energy level, or the spacing between energy levels, will likely change when you have a material structure which will confine those particles, like electrons and atoms. ( 2 ) High interface area, where the number of atoms at an interface becomes very large. For a polycrystalline material, when the diameter of the crystals (e. g. , grains) is on the order of microns, the fraction of atoms at the interface is only on the order of a half percent. As the dimension of the grain is reduced, the fraction of atoms at the interface increases quickly. For example, Ref. [l] shows that at a crystal size of 3 n m , between 40% and 60% of the atoms are at the interface. ConsequentBi0graphy:Robert D Shull(1946-1, Male, Doctor, Engineer;

ly, at large grain sizes, the properties of the material will be closely related to the properties of the atoms interior to the grains. Conversely, at small grain diameters, the material properties will be related t o the properties of the interface atoms. ( 3 ) Closeness of the material lengths t o the critical length scale of the property. Every property has a critical length scale associated with that property (e. g. , the mean free path in electrical and thermal conductivity, diffusion length in atomic transport, wavelength in scattering behavior, penetration depth in absorption, and half-life in radioactive decay processes) , and material behavior will typically change when a material length scale becomes comparable with that property length scale. For magnetism, Table 1 (from J. M. D Coey) gives some of these critical length scales and their values for a common soft ferromagnet like Fe and a h a r d ferromagnet like Nd,Fe,,B. In this table, A is the exchange constant, po is the permeability of free space, J is the exchange integral, K is the anisotropy, k B is the Boltzmann constant, and T is the temperature. Note that most of these length scales are in the nanometer range. Consequently, one would expect the bulk magnetic character of a nanostructured ferromagnetic
Revised Date: November 2 7 , 2006

E-mail: ShullBnist. gov;

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Journal of Iron and Steel Research, International

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nm

Table 1
1,engt h Exchange length Coherence radius Domain wall width Single-domain size

Magnetic length scales

Symbol
1P I
Rcoh

Definition

Fe
1.5 7
40
6

Ndz Felr B

J,GmF

1. 9
9 3. 9

J241,,
X L I K

6w

Superparamagnetic blocking radius ( a t 300 K )

Rso RB

36~1,.
(6ks T / K )

107

1. 7

material to change from that of such a material without t h e nanometer-sized material dimensions. T h e types of material dimensions which might be important would include t h e particle size in a particulate material, t h e separation distance between those particles, the grain size of a material, the layer thickness or separation distance between layers in a layered material, t h e thickness of a secondary phase a t a grain boundary. t h e fiber diameter and separation distance between fibers in a fibrous material, and t h e surface irregularity at interfaces. For composite materials containing nanomctcrsized species, one of which ( M ) is ferromagnetic and one of which ( N ) is non-magnetic mixed together, one can even plot a magnetic phase diagram a s shown in Fig. I . Note that t h e Curie point drops precipiV tously a t some composition of . (typically when percolation of the t w o species o c c u r s ) , and that for all greater concentrations of N there is a completely new magnetic state called superparamagnetism . Superparamagnetism requires nanometer-sized ferromagnetic entities magnetically decoupled from each o t h e r , a s would occur by physically separating t h e m via t h e non-magnetic species. In this magnetic s t a t e , there is no permanent magnetic memory after applying a magnetic field, even though its magnetic s u s ceptibility can be rather large. Since high density magnetic recording media is this type of composite structure. when t h e ferromagnetic particle size gets small enough, t h e material would possess this magnetic state and lose its ability t o store any information. For other applications. like magnetic cooling, this typc of magnetic state can actually give a n increased cooling capability. One of t h e main uses of a ferromagnet is a s t h e core in a transformer. T h e area enclosed in t h e hysteresis loop for that material indicates t h e work required to make o n e complete cycle of t h e field. F o r a transformer core, t h e current in t h e primary coil ( 2 , ) is alternating direction, and therefore creating a n alternating field direction. Consequently, t h e magnetization of t h e transformer core traces out a hysteresis

Paramagnetic

-Superparamagne tic
i-

Ferromagnetic

Magnetic species (

03

0.5 Vol. fract. N

0.7

(Y1 .
Fig. 1

Non-magnetic species (N)

Magnetic phase diagram

loop each of t h e many cycles per second dictated by t h e frequency of il , and during each cycle t h e energy indicated by t h e area enclosed in t h e loop is converted into heat. T h a t heat m u s t subsequently be removed. Consequently, one w a n t s to use a ferromag net which has very little area inside i t s hysteresis loop, which means i t should have a small coercivity ( H c - ) . In order to have a low H c value, t h e ferromagnet should be able t o reverse its magnetization easily. T h e easiest mechanism whereby t h e magnetization can be reversed is by nucleating a small local region, called a domain, having that reversed magnetization and t h e n rotating only t h e magnetic spins at t h e boundary of. that domain while that boundary wall moves through t h e material. Therefore, the ease in reversing t h e total magnetization upon field reversal is dependent upon how easily t h e domain walls are moved. If something stops t h e motion of a wall, it is called a pinning site, and very effective pinning sites a r e grain boundaries i n conventional materials. I n order to overcome t h e pinning force ol those special sites, a greater field is required, leading to a higher coercivity. Since grain boundaries are good pinning sites, if t h e grain size is reduced, the coercivity increases ( a s s h o w n at t h e large grain di-

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ameter region in Fig. 2c21) due to the larger number of pinning sites. However, when the grain size becomes comparable to the width of the domain wall (e. g. , in nanocrystalline materials) then the grain boundaries become less effective as pinning sites; further decrease in grain size results in a lowering of the coercivity to some of t h e smallest values yet achieved. Another major application of ferromagnetic materials is in magnetic recording devices, both as the media and in the read and write heads. For the media, one wants each region wherein information is stored and retrieved to be as small as possible. At the same time each region of stored information needs to be decoupled from neighboring regions. There is a lower limit, however, on how small one can make these ferromagnetic cells. As described above, when one decouples nanometer sized ferromagnetic entities from each other, the material will sooner or later become a superparamagnet. At that point, the material would not retain any magnetic information since it has no remanent magnetization when the external field is removed. Consequently, that size represents a lower bound to the lateral size of the ferromagnetic regions in the media. There is another problem with very small size recording bits. As the size of those regions decreases, so does the magnetization of those regions and also the magnitude and extent of the magnetic fields emanating from them. Therefore, one needs a device sensitive enough to read those smaller field values. Luckily, in 1988, there was the discovery of a new nano-magnetic phenomena called the giant magnetoresistance effect (GMR) wherein a structure con100

10

r\

3 s
2 -

0.1

0.01

Permalloy ==

>

0.001 I

1NIl

1 P %rainsize

1m m

Fig. 2

Coercivity vs grain size for several materials

sisting of two thin ferromagnetic ( F M ) layers separated by a very thin (1 nm) non-magnetic lajrer was found to possess very large resistance changes when the magnetization direction of the two ferromagnetic layers changed from being antiparallel to parallel~31. T h e effect arises from spin dependent scattering of the electrons, resulting in very long mean free paths for only those electrons with the same spin state as the ferromagnet in which it is moving. If both ferromagnetic layers are similarly magnetized, the structure allows electrons with one state to short circuit the device, leading to a significantly reduced resistance. These structures are now used as sensitive detectors of magnetic fields, and operate as the read heads (in a spin valve configuration) on present day magnetic hard disks. One critical element in the spin valve structure is the use of another nano-magnetic effect: a thin antiferromagnetic ( A F ) layer placed next to one of the GMR ferromagnetic layers in order to pin the direction of magnetization of that FM to some fixed direction. Such a bilayer couple is known to shift the magnetic hysteresis loop of the F M along the field axis, thereby giving the material a magnetic field bia s , called an exchange bias (coming from the magnetic exchange interaction between the AF and ) FMC4 . For permanent magnets, reduction of some material parameter to the nanoscale is also being found to be important. The idea here is to increase the energy product (i. e. , the area enclosed in the hysteresis loop) of a hard ferromagnet by replacing some of its high coercivity material which has a low saturation magnetization ( M , ) by a low coercivity soft ferromagnet which has a high M s value. Such a replacement is expected to give a larger energy product since the exchange interaction between the hard and soft ferromagnet would be expected to be so strong that magnetization reversal would not occur by the nucleation of local regions of reversed magnetization, but instead via the coherent rotation of the magnetic moments, a much more difficult process!;. If the thicknesses of the individual species are on the order of the domain wall width of the hard ferromagnet (i. e. , in the nanometer range as shown in Table 1) , this rotation would be continuous. Proof of this reversal prediction was found by means of using the magneto-optic indicator film (MOIF) technique developed at NISTC6.71. this In technique, a polarized light beam passes through an

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in-plane magnetized thin film with a large Faraday effect placed on top of the sample. Where there is flux leakage from the sample. like at a domain wall and sample edge, the polarization of that light beam is rotated differently (since the film magnetization will be locally perpendicular), and thereby providing a contrast to neighboring regions when viewed through a polarized analyzing crystal. When applied to observing the magnetization reversal in a hard/ soft ferromagnet bilayer the pictures shown in Fig. 3 for fields ( H I slightly off the easy magnetization ( M ) axis of the material were obtained. In this figure, since there is no domain wall perpendicular to the film plane, no image is obtained of that domain wall. Consequently, a hole was drilled through the film, and the direction of M is obtained from the black line drawn through the hole connecting the points of maximum darkness and brightness on the inside edge of the hole where magnetic poles of opposite sign have been created by the magnetization vector of the surrounding region. Note that when the reversing field is aligned slightly off the easy magnetization axis, M rotates in proportion to the field magnitude, either clockwise ( C W ) or counterclockwise (CCW) , depending upon whether H is oriented counterclockwise or clockwise with respect to M ; this proves the coherent rotation model. Higher energy products than the best Nd2Fe14 permanent magnets have even B been obtained using this methodology:.:.

Fig. 3

MOlF images of a Fe/SmCo bilayer as a reversed H is applied in plane of film

A future large application envisioned for magnetic materials is the area of refrigerationC8. The main advantage of magnetic refrigeration is that it is based on a reversible process and thereby makes Carnot efficiencies possible. In the past, i t had the connotation of being a very low temperature ( T ), high magnetic field process. However, in the past 10 years, there have been advancements which have moved the idea of low field high temperature units out of t h e realm of science fiction. Specifically, new alloys, like Gds Ge, Si2[, L a ( F e 2 L )13r101 , La, Sr,.zMnQ[ , MnFePo.45 Aso.5521 , and Gd, Ge2-l Si, have been discovered with large magnetocaloric effects ( A S or MCE) near 300 K , and new refrigerator designs have been developed for high temperature application. For low temperatures, magnetic nanocomposites are particularly attractive as refrigerant^"^]. If the magnetic moments in a material are grouped together in nanometer-sized clusters which are decoupled from each other, the material will form the new magnetic state of superparamagnetism. In this s t a t e , there will be an enhancement of t h e magnetocaloric effect over that obtained if one had independent magnetic spins in the materialCj2. T h e enhancement in entropy is shown in Fig. 4, a s calculated for a system containing only spin 7/2 atoms, e. g. Gd atoms, after a field application of 800 k A / m (1 T). Note, a t low T the A S as. T curves cross, showing t h e single spin case has higher A S values at T less than the crossing point. T h a t situation occurs when magnetic saturation of the spins is approached, and that is a situation which is virtually inaccessible in a magnetic refrigerator. However, at all T higher than the crossing point, the clustered material has larger A S values than the independent spin case. Also note that for whatever temperature and field the refrigerator is t o be operated, there is an optimal cluster size that gives the highest A S values. Paramagnetic gadolinium gallium garnet (GGG, the best low temperature magnetic refrigerant), shows this enhancement when magnetic clusters are formed in it after the addition of a few Fe atoms in place of Ga. Superparamagnetism in Gd3Gas-, Fe,OiZ results because of the presence of a magnetic superexchange interaction between t h e new F e spins and neighboring Gd spins. Fig.5 shows the entropy change for a 800 k A / m field change as a function of temperature measured for the Gd3Gas-I Fe,Ol2 nanocomposite and GGG. Note the superparamagnetic materials (indicated by the top two curves) possess significantly enhanced

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Nanocrystalline and Nanocomposite Magnetic Materials and Their Applications

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1.0

-Spin 7/2 atoms -_--

10 atom clusters

0.8

-$

0.6

0.4

0.2

Fig. 4

Magnetic entropy change vs temperature for a superparamagnet with indicated cluster sizes

2.4
2.0

i
\I

pizGq

1.6

I I\

\vx=2.5

g k

1.2

3 0.8

0.4

TemperatureK Fig. 5 Magnetic entropy change vs temperature for GGG and Gd, Ga+x FexOl2nanocomposites

ate electronic devices, called " spintronic" devices, wherein the conduction of electrical current is controlled by the spin density of states of dissimilar materials placed adjacent to each other, rather than by the charge density of states upon which all present day electronics is Consequently, there is much interest in developing a ferromagnetic semiconductor, for instance, with a Curie temperature above 300 K. With such materials, it is envisioned one would be able to change the transmission of current remotely (without contacts) by applying a magnetic field. Such materials would have infinite switching capability, be scaleable to small sizes using existing CMOS technology, and would enable fewer transistors in logic circuits, possibly even enabling quantum computing. In summary, there are a number of new magnetic properties possessed by materials having some critical material length scale in the nanometer range. Compared t o conventional materials, they may possess smaller size (for greater storage density media), GMR effects (thereby possessing higher sensitivity for magnetic fields for sensor applications) , lower coercivity (for next generation transformer materia l s ) , higher coercivity ( for improved permanent magnets 1, superparamagnetic character ( for improved magnetic imaging in magnetic force microscope systems) , and enhanced magnetocaloric effects (for potentially enabling high temperature and low magnetic field refrigerators) as examples. Although not described here, they may also possess light transparency (for advanced color toners) and larger Kerr effects (for magnetcoptic data storage application).
References:
Siege1 R. [J]. Annu Rev Mater Sci, 1991, 21: 559. Herzer G. Grain Size Dependence of Coercivity and Permeability in Nanocrystalline Ferromagnets [J]. IEEE Trans Magn, 1990, 2 6 ( 5 ) : 1397-1402. Baibich M N , Broto J M, Fert A , et al. [J]. PRL, 1988, 61: 2472. Nikitenko V I, Gornakov V S, Dedukh L M , et al. [JI. Phys Rev, 1998, 57B(14): R8111. Kneller E, Hawig R. T h e Exchange-Spring Magnet: a New Material Principle for Permanent Magnets [J]. IEEE Trans Magn, 1991, 27(4): 3588-3560. Jiang J S, Fullerton E E , Sowers C H , et al. Spring Magnet Films [J]. IEEE Transactions on Magn, 1999, 35(5) : 32293234. Shull R D, Shapiro A J . Gornakov V S, et al. [J]. IEEE Transactions on Magnetics, 2001, 37(4) : 2576. Barclay J A , Steyert W A. [J]. Cryogenics, 1982. 2 2 : 73. Pecharsky V K , Gschneidner K A. [J]. J r Phys Rev Lett,

A S values as predicted. GGG ( t h e bottom curve) is useful up to 15 K , so its entropy change at 15 K represents how much is needed t o operate a magnetic refrigerator. Note the top curve possesses at least that much entropy change to T values a factor of 45 times higher. Therefore, this route shows how this technology may be increased to much higher T values. Alternatively, since at 15 K the top curve has a value 3 - 4 times that of GGG, one can also think of using this route for reducing the magnetic fields to those possible by permanent magnets rather than 5 T superconducting systems requiring cooling to 4 K. Another area of great excitement is the combining of electronic and ferromagnetic materials to cre-

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1997, 78: 4491-4497. Fujita A , Fujieda S. Hasegawa Y , et al. Itinerant-Electron Metamagnetic Transition and Large Magnetocaloric Effects in La(Fe,Sil-.)1,, Compounds and Their Hydrides-Art. No. 104416 [J]. Phys Rev, 2003. 6 7 ( 10): 4416. Llohigas X , Tejada J + del Barco E , et al. Tunable Magnetocaloric Effect in Ceramic Perovskites [J]. Appl Phys Lett, 1998, 7 3 ( 3 ) : 390-392. Tegus 0, Bruck E. Buschow K H J . et al. Transition-MetalBased Magnetic Refrigerants for Room-Temperature Applicatiom [J]. Nature. 2002. -115(6868): 150.152. Provenzano V. Shapiro A J . Shuli R D. Reduction of H y s t e r e

[1 4 3

C15l

sis Losses in the Magnetic Refrigerant GdsGezSiz by Theaddition of Iron [J]. Nature, 2004, 429(6994): 853-857. McMichael R D, Shull R D, Swartzendruber L J , et al. IJ]. J Mag and Magn M a t , 1992, l l l ( 1 - 2 ) : 29. Shull R D, Swartzendruber L J , Bennett I, H. Proceedings of the Sixth International Cryocoolers Conference [C]. G Green,

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Conclusions

T h e addition of Cu-10% alloy for developing t h e high strength 465 mara ging stainless steel from elemental powders was investigated. 3 % Cu-10% alloy enhances t h e sintering process and t h e densification of 465 stainless steel. Sintering t o 7. 4 g/cm3 is only possible with 3 % Cu-1OSn alloy at 1 300 "C for 60 min. T h r e e mass percent Cu-1OSn alloy addition increases t h e sintered density and t h e ultimate tensile strength. T h e ultimate tensile s t r e n g t h of 517 MPa was achieved with t h e product containing 3 % Cu-10% alloy.
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Ll_
_ .

[2;

Chiaverini V. Sintered Stainless Steels [.4_1. Campus J M. German R M. eds. Advances in Powder Metallurgy and Particulate Materials [C:. Princeton: MPIF. 1992. 359-372. Molins C. Bas J .4. Planas J , et al. P / M Stainless Steel: Types and Their Characteristics and Applications [A;. Campus J M. German R M , eds. Advances in Powder Metallurgy and Particulate Materials [C]. Pnnceton: MPIF. 1992. 345-357.

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