Journal of Magnetism and Magnetic Materials 200 (1999) 373}391

Nanophase hard magnets

George C. Hadjipanayis*
Department of Physics and Astronomy, University of Delaware, Newark, DE 19716, USA
Received 17 March 1999; received in revised form 29 April 1999

Abstract

The dramatic developments that occurred in nanophase hard magnetic materials over the last two decades are
reviewed. Much of the research was done after the discovery of Nd Fe B-based magnets in an attempt to develop more
 
economical Fe-based magnets with better properties. This led to the discovery of 1 : 12-based magnets, 2 : 17 nitrides and
carbides, and more recently, to nanocomposite magnets consisting of a "ne mixture of exchange coupled soft and hard
phases. Currently, much emphasis is devoted to nanocomposite "lms consisting of nanoparticles of a high anisotropy
material embedded in a non-magnetic matrix because they have a great potential for applications in high density
recording media.  1999 Elsevier Science B.V. All rights reserved.

Keywords: Permanent magnet; Nanophase; Microstructure; Coercivity

1. Introduction the 1950s with the discovery of single domain mag-

Nanophase materials have attracted consider-
able interest in the last few years because of their
unusual scienti"c and technological properties
[1}5]. These properties are di!erent from those in
bulk for particle/grain sizes in the nanometer scale
because of size and surface/interface e!ects [1]. In
magnetic materials, these properties are exploited
in a number of applications including soft magnets
[2], permanent magnets [3], magnetic recording
[4,5] and have potential in magnetic refrigeration
[6]. This article is focused on hard magnetic mate-
rials.
The motivation in research in nanophase hard
magnetic materials originates from the size depend-
ence of coercivity H (Fig. 1) which was known in

* Tel.: #302-831-2736; fax: #302-831-1637.
E-mail address: hadji@udel.edu (G.C. Hadjipanayis)
netism [7]. According to this behavior, the coerciv-
ity of powdered magnets increases with the
reduction of particle size going through a max-
imum at the single domain size and then decreases
again for ultra"ne particles due to thermal e!ects
and becomes zero at the superparamagnetic par-
ticle size. For strongly anisotropic materials with
reasonably high magnetization, the single domain
particle size is a fraction of a micron (Table 1) and
therefore, when materials are made with micro-
structure of this size, their coercivity is enhanced.
The "rst studies on nanophase magnetic systems
were made on amorphous R}Fe (R"Tb, Sm)
alloys which, upon crystallization, led to nanosize
particles with the Laves RFe phase with large

coercivities at room temperature [8]. In the late
1970s, a global cobalt crisis occurred, which led to
intense research to discover Fe-rich magnets with
a focus on Pr(Nd)-Fe alloys. The breakthrough
came in late 1983 when Hadjipanayis et al. [9,10]

0304-8853/99/$ - see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 8 8 5 3 ( 9 9 ) 0 0 4 3 0 - 8
374 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391

alloying [24,25] for the fabrication of nanophase


Fig. 1. Size dependence of coercivity.
and Croat et al. [11] using melt-spinning, were able
to obtain large H on melt-spun Pr}Fe}B(Si) and

Nd}Fe}B alloys, respectively. The large coercivities
in both of these systems are due [12] to the highly
anisotropic tetragonal R Fe B phase (K"
 
4.5;10 erg/cm) which was produced in the
nanoscale size during melt-spinning, or after crys-
tallization [13]. This discovery opened new hor-
izons for magnetic materials research, and
revolutionized the world of permanent magnets.
Since then, many other systems including the 1 : 12,
2 : 17, 2 : 17N(C) , 3 : 29, 1 : 5, etc. have been made
6
with nanosize microstructure and with large values
of coercivity [14}18]. Also, besides melt-spinning
and splat cooling, other rapid solidi"cation tech-
niques have been used like vapor deposition
[19}22], atomization [23], and mechanical
magnets. Recently, sputtering techniques have also
been used to prepare nanosize Sm}Co alloys [5,26]
and CoPt and FePt alloys for high density record-
ing media [27,28].
The maximum energy product (BH) , which
characterizes the strength of a magnet, depends
strongly on the remanent magnetization M with

a theoretical value (BH) "(4pM /2) [29].
Nanophase magnets usually consist of randomly
oriented uniaxial grains, and therefore, their re-
manence is M "M /2 leading to lower values of
 
(BH) as compared to anisotropic sintered mag-
nets. Therefore, additional processing like sintering
[30], or die-upsetting [31], is required to increase
the remanence and (BH) of these materials. In the
past, several attempts have been made to increase
the remanence in melt-spun Nd}Fe}B materials. It
was "rst found that Nd}Fe}B magnets containing
small amounts of Si and Al had high reduced
remanence m "M /M , greater than 0.5 in an iso-
  
tropic material [32]. The high remanence was re-
lated to a uniformly "ne microstructure consisting
of small (18 nm) 2 : 14 : 1 grains with clean grain
boundaries [33]. Later, however, Manaf et al. [34]
showed that the presence of Si and Al was not
necessary for the high remanence in Nd}Fe}B rib-
bons, and attributed the results to a controlled
microstructure having small grains ((30 nm). The
high remanence is attributed to a net alignment of
grain magnetization caused by strong intergrain
exchange interactions. Higher values of remanence

Table 1
Magnetic properties of nanocrystalline magnets

Magnet M (kG) H (kOe) D (lm) ¹ (3C) H (kOe) Ref.

    
Nd Fe B 16.0 67 0.25 315 15 [11]
 
Pr Fe B 15.6 87 292 12 [74]
 
Tb Fe B 6.64 220 1.69 356 96 [43]
 
Dy Fe B 7.12 150 320 64 [43]
 
Pr Co B 9.75 100 717 25 [45,52]
 
Sm Fe Ti 11.7 105 311 3.7 [45,46]
  
Sm Fe V 8.0 54 337 10 [25,46]
  
Sm Fe N 15.4 140 0.36 470 30 [46]
  

Sm Fe C '100 400 23 [46]
  

Sm Co 12.5 52 920 9 [40,53]
 
SmCo 11.4 240}440 0.71}0.96 727 50 [15,40]

 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
were subsequently achieved in nanocomposite
magnets consisting of a mixture of exchange-
coupled hard and soft phases. Coehoorn et al. [35],
produced a high reduced remanence of 0.8 with
a coercivity of 4 kOe in melt-spun Nd Fe B
  
alloys consisting of Fe B and Nd Fe B phases.
  
Ribbon samples containing mixtures of
Nd Fe(Co) B#a-Fe (Co) and Pr Fe(Co) B#
   
a-Fe(Co) were also shown to develop high reduced
remanence and coercivity [36]. Since then other
systems have been found, including Sm}Co [37],
Sm (Fe,Co) N [38], and Sm (Fe,Co) C [39].
  6   6
Reasonable values of coercivity can be realized in
such mixtures, even with 10 vol% of the hard
phase.
Another class of nanocomposite materials is the
precipitation hardened 2 : 17 magnets with com-
position Sm(Co,Fe,Cu,Zr) [40]. The complex
X
microstructure of these bulk magnets consists of
a "ne mixture of cellular (with 2 : 17 cells sur-
rounded by 1 : 5 walls) and lamellar patterns (Z-
phase) [41]. The interplay between the size and
chemical composition of these phases controls both
the magnitude and temperature dependence of co-
ercivity.
The title chosen for this article is very broad and
can include many di!erent examples of novel mag-
netic materials. The present article is focused on
bulk materials, primarily on cast samples, ribbons,
powders, and covers single-phase nanocrystalline
and two-phase nanocomposite magnets, including
the exchange and precipitation hardened 2 : 17
magnets. The only section referring to thin "lms is
on granular solids with high anisotropy for high
density recording media (CoPt(FePt)/C(Ag) and
SmCo (Nd Fe B)/W). Special emphasis is given
  
to the role of particle/grain size in the property
microstructure relationship.
2. Nanocrystalline single-phase materials
In the 1980s, nanocrystalline rare earth inter-
metallic compounds were used as a quick tool in
the search of new anisotropic phases for permanent
magnets by simply crystallizing the amorphous
precursor and checking the coercivity of crystalliza-
tion products [42]. In fact, the 2 : 14 : 1 phase was
375
found this way [9,10]. It was soon realized that
these materials have a high coercivity that is much
larger than that corresponding to bulk magnets,
including sintered magnets. For example, melt-
spun Nd Fe B samples can easily attain coercivity
 
beyond 15 kOe (Table 1), while the coercivity of
corresponding sintered magnets is below 10 kOe.
The higher the anisotropy of the material the larger
the coercivity is expected to be. In Tb Fe B and
 
DyFe B with H "220 and 150 kOe, respectively,
 
coercivities in excess of 60 kOe have been reported
[43]. Large values of coercivity can also be ob-
tained in the R Fe C system, but their processing
 
is more subtle because of a phase transformation in
the system from Nd Fe C to Nd Fe C [44].
  6  
The system must "rst be made into the primary
Nd Fe C soft phase with planar anisotropy be-
  6
fore being transformed into the anisotropic
Nd Fe C.
 
After the discovery of the R Fe B(C) com-
 
pounds with large coercivities in crystallized melt-
spun ribbons, other compounds were made in the
nanocrystalline state and their magnetic properties
are listed in Table 1. The Sm(Fe,M) tetragonal

compounds were stabilized by small substitutions
of M"Mo, Ti, V, and also had large values of
coercivity [45]. Later, the strongly anisotropic
Sm Fe N and Sm Fe C were discovered by
  6   6
the interstitial gas modi"cation (IGM) process [46]
with N and or C, and were also produced in the
nanocrystalline state [47]. The nitrogenation/car-
bonation process was also applied to other systems
and the resulting properties are shown in Table
1 [48].
2.1. Microstructure
The single-phase materials have a chemical com-
position very close to the stoichiometric composi-
tion of the hard magnetic phase to minimize the
presence of secondary phases. The nanocrystalline
state is usually obtained by rapid solidi"cation
techniques and by mechanical alloying. In the for-
mer, the nanostructure is obtained either by crys-
tallizing the precursor amorphous alloy, formed by
melt-spinning, splat-cooling, and double roller, or
in situ by varying the cooling rate of the process
used [49]. In the latter, annealing is always
376 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
Fig. 2. Crystallization behavior of Nd}Fe}B}Nb ribbons as
seen by DSC.
required to crystallize the amorphous structure
produced by mechanical alloying either of the cor-
responding single elements or of alloy powders.
The annealing temperatures are usually higher
than the crystallization temperatures in all of the
materials studied. Fig. 2 shows a typical di!erential
scanning calorimetry (DSC) run for Nd}Fe}B}Nb
where the strong exothermic peak indicates the
onset of crystallization at a temperature close to
6103C. (For pure Nd Fe B, the temperature is
 
closer to 5803C.) This is much lower than the usual
annealing temperature for the optimum properties
which is in the range of 700}8003C. The reasons for
this are that the higher temperature annealing leads
to a microstructure with an optimum size for mag-
netic hardening, and to the disappearance of
a-Fe(Co) which is usually the "rst product of crys-
tallization.
The microstructure of single-phase materials is
fairly uniform, consisting of randomly oriented
grains of the hard magnetic phase as shown in
Fig. 3. The c-axis of these phases (compounds) is the
easy axis of magnetization. The grain boundaries
are clean and free of other phases [12,13]. This is
di!erent in o!-stoichiometric alloys where minor
phases (mostly R-rich) are observed at grain
boundaries, especially at triple grain boundary
junctions [50]. High coercivities can easily be ob-
tained with grain sizes below 80 nm. This size is
Fig. 3. Typical microstructure of nanocrystalline Nd Fe B.
 
usually below the single domain particle size which
for most of the high anisotropy materials is a frac-
tion of 1 lm (Table 1). Magnetic domain studies
[51], in fact, showed domain walls clustering
around the grain boundaries (Fig. 4a), indicating
again that each grain is a single domain. In the "ner
grain size ((40 nm) ribbons, besides the large H ,

an enhanced reduced remanence (m '0.5) is ob-

served in isotropic samples. This is usually accom-
panied by the presence of large domains (Fig. 4b)
referred to as &interaction domains' [51] (contain-
ing many nanograins), and is the result of exchange
interactions among the spins of adjacent grains
which pull the easy axis away from the grain c-axis
leading to larger regions with a net magnetic align-
ment.
2.2. Magnetic properties
The shape of the hysteresis loop of nanophase
magnets is highly sensitive to their microstructure
[52]. Typical hysteresis loops of melt-spun and
heat-treated samples are shown in Fig. 5. In the
overquenched state, the sample is amorphous and
magnetically soft. The high coercive state is usually
achieved either by annealing the overquenched
sample, or by varying the speed of the wheel, to
reduce the cooling rate and obtain the typical opti-
mum microstructure shown before. In the under-
quenched state, the sample contains large grains
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
Fig. 4. (a) Magnetic domains in nanocrystalline Nd Fe B and
 
(b) interaction domains (ID).
Fig. 5. Hysteresis loops of as-spun and heat treated Nd Fe B.
 
with low H . However, our recent studies on under-

quenched samples, which were further annealed,
surprisingly showed a much "ner microstructure
that led to the highest coercivity observed.
The loop corresponding to the optimum state
shows an initial curve characteristic of single-
377
domain particles. Because of the random distribu-
tion of grain orientations (and domains), a large
high "eld susceptibility is observed, and the satura-
tion magnetization can only be determined by us-
ing the law of approach to saturation [7]. The
reduced remanence m of these samples is close to

0.5 indicating the absence of domain wall motion.
Higher values of m are only observed in samples

with much "ner microstructure due to intergrain
exchange interactions as discussed earlier.
2.3. Magnetic hardening
The "ne and non-uniform microstructure of rib-
bons makes it di$cult to discuss their magneti-
zation reversal in terms of pure pinning and/or
nucleation models [53]. The former has been sug-
gested based on the shape of initial curves and
"eld and temperature dependencies of coercivity
[54,55]. Durst and KronmuK ller [56], on the other
hand, argued in favor of the nucleation model from
their H (¹) data. The hysteresis behavior of these

grains is more characteristic of interacting single-
domain particles where the interactions among the
domains of adjacent grains in#uence their reversal.
Indeed initial magnetization and remanence curve
measurements [57] showed that magnetization re-
versal in the latter grains occurs by #ipping the
moment of a few grains at a time. The magneti-
zation reversal processes in the "ne-grained mag-
nets can be [58] explained better using the random
anisotropy and micromagnetic models discussed in
Section 3.1.4. The interactions are much stronger in
smaller grains (below 20 nm) and this leads to the
&interaction domains'. The coercivity in the latter is
probably controlled by the motion of domain walls
in the &interaction domains'.
3. Nanocomposite magnets
3.1. Exchange coupled magnets
Nanocomposite exchange coupled magnets con-
sisting of a "ne mixture of magnetically hard (to
provide high coercivity) and soft (to provide high
magnetization) phases have attracted much atten-
tion for potential permanent magnet development.
378 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391

The exchange coupling causes the magnetization

vector of the soft phase to align with that of the
hard phase, leading to an m above 0.5 in a crystal-

lographically isotropic structure along with a rea-
sonable coercivity. Because of this, a higher (BH)

would be expected in exchange coupled magnets as
compared to the conventional isotropic uncoupled
magnets. In addition, nanocomposite magnets are
of commercial interest because the costly magnetic
alignment step is not required and the magnets
contain less of the expensive rare earth element. Up
to date, several nanocomposite magnet systems,
including Nd Fe B/Fe B [35], R Fe B/Fe [36,
    
59}62] R Fe C/Fe (R"Nd, Pr) [63], Sm Fe N /
    6
Fe [38], Sm Fe C /Fe [64] and Sm (Co,Fe) /
  6  
(Co,Fe) [65], have been extensively studied. The Fig. 6. Typical hysteresis loops of nanocomposite Nd}Fe}B
usual processing techniques to synthesize bulk magnets.
nanocomposite magnets are melt-spinning [36]
and mechanical alloying [25].
the optimum (BH) . The exchange hardened iso-

3.1.1. Magnetic properties tropic magnets are characterized by smooth hyster-
Nanocomposite magnets have an o!- esis loops with a high value of remanence (m '0.5)

stoichiometric composition, Fe or Co-rich, which despite the large amount of the soft phase (Fig. 6).
usually leads to a two-phase microstructure con- The magnetic properties of various systems are
sisting of magnetically soft a-Fe(Co) and the hard shown in Table 2. In most systems studied the
phase of the system of interest [66,67]. The larger reduced remanence is greater than 0.6. The value of
the amount of the soft phase the higher the magne- reported coercivity depends strongly on the
tization (remanence). This, however, comes at the amount of the hard phase and it is in#uenced by
expense of coercivity that is signi"cantly reduced. both the intrinsic properties of the hard phase and
The proper choice of composition usually leads to the sample microstructure. This is clearly seen in

Table 2
Magnetic properties of nanocomposite magnets

Magnet composition Hard/soft phase M (kG) M /M H (kOe) Ref.

   
Nd Fe B Nd Fe B/Fe B 12.0 0.7 3.6 [35]
     
Nd Fe Nb B Nd Fe B/Fe 10.4 0.67 3.8 [36]
     
Tb Fe Nb B Tb Fe B/Fe 4.2 0.5 1.0 [36]
     
Dy Fe Nb B Dy Fe B/Fe 4.3 0.5 1.0 [36]
     
Pr Co Nb B Pr Co B/Co 9.0 0.6 4.3 [36]
     
Pr Fe B Pr Fe B/Fe 14.2 0.68 4.9 [62]
    
Pr (Fe Nb ) B Pr Fe B/Fe 12.2 0.69 9.0 [62]
 
 
    
Pr ((Fe Co ) Nb ) B Pr (Fe,Co) B/(Fe,Co) 13.8 0.67 2.1 [62]
 
 
 
 
    
Pr ((Fe Co ) Nb ) B Pr (Fe,Co) B/(Fe,Co) 11.2 0.71 6.5 [62]
 
 
 
 
    
Sm Fe Cr C Sm Fe C /Fe 8.6 0.57 12.1 [64]
      6
Sm Fe Co Cr C Sm (Fe,Co) C /(Fe,Co) 8.5 0.63 9.7 [64]
       6
Sm Fe N Sm Fe N /Fe 14.0 0.79 3.9 [38]
  6   6
Sm Co Fe Sm (Fe,Co) /(Fe,Co) 15.3 0.78 3.9 [65]

 
   
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
Fig. 7. Recoil demagnetization curves in exchange hardened
Nd}Fe}B spring magnets.
R Fe Nb B samples with R"Tb or Dy whose
   
coercivity is much lower (1 kOe) than that of the
melt-spun Nd Fe Nb B samples despite the
   
huge anisotropy of the R Fe B (R"Tb, Dy)
 
phases [43]. This is attributed to the larger a-Fe
grains in these samples because of their higher
annealing temperatures necessary to form the hard
R Fe B phase.
 
An interesting property of these magnets is
the large degree of reversibility [66,68] in their
demagnetization behavior due to exchange coup-
ling, leading to a referral of these magnets as
&spring magnets'. This is shown in Fig. 7 for
Nd Fe Nb B where the change in M is very
    
small for "elds up to 2.6 kOe. For higher "elds
irreversible rotation takes place leading to a rapid
decrease in M .

Another interesting behavior of exchange
coupled magnets is the enhancement of Curie tem-
perature of the hard phase due to the exchange
coupling e!ect. Lewis et al. [69] and Dahlgren et al.
[70] have observed an enhancement in the Curie
temperature of the R Fe B phase in R Fe B/Fe
   
nanocomposite magnets. A more signi"cant enhance-
ment has been observed in the Curie temperature of
the 2 : 17 phase in exchange-coupled melt-spun
nanocomposite Sm (Fe,Co) Cr C /(Fe,Co) mag-
   
nets (273C in Sm Fe Cr C and 1023C in
   
Sm Fe Co Cr C ) as compared to their parent
    
cast alloys [71]. The enhancement in Curie temper-
ature is believed [72,73] to be the result of the
379
Fig. 8. E!ect of decoupling of soft and hard phases on the
demagnetization curves.
penetration of the exchange "eld of the higher
Curie temperature phase into the adjacent lower
Curie temperature phase. This leads to an increase
of the average e!ective molecular "eld of the latter
phase resulting in a spontaneous magnetization at
temperatures above its normal Curie temperature.
The exchange coupling is strongly temperature
dependent, and because of this, in some systems the
two phases become decoupled at low temperatures
[36,74]. This e!ect is more pronounced in
Pr Fe Nb B as shown in Fig. 8. The loop mea-
   
sured at 300 K has a smooth demagnetization
curve, in contrast to the loops measured at lower
temperatures which contain a shoulder that is more
pronounced as the temperature is lowered. The
coercivity of these systems has contributions from
both the 2 : 14 : 1 grains and a-Fe that is hardened
by the exchange coupling. The 2 : 14 : 1 coercivity,
however, is increased rapidly at low temperatures
because of the drastic increase of the anisotropy
K of the 2 : 14 : 1 phase. On the other hand, the
coercivity of exchange hardened a-Fe is increased
slightly leading to the observed shape of the demag-
netization curve (Fig. 8).
3.1.2. Microstructure-property relationship
It has been demonstrated by both theoretical
analysis [68], and micromagnetic modeling simula-
tions [75}77], m that the magnetic properties of
nanocomposite magnets depend strongly on the
380 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391

intrinsic magnetic properties of the phases present

and on the microstructure features. Earlier studies
by Kneller and Hawig [68] showed that in such
a microstructure the hard and the soft phase would
be exchange coupled if the sizes of both the soft and
the hard phases are in the order of twice the domain
wall-width of the hard phase, which is less than
10 nm for most hard phases. Fischer et al. [77]
predicted that M and H decrease with increasing
 
grain size and that the magnetic properties are
degraded by a non-uniform microstructure. There-
fore, it is very important to develop a uniform
microstructure with very "ne soft phase grains,
uniformly distributed in the nanocomposite mag-
nets, in order to obtain optimum coupling. This can
be achieved by optimizing both the composition
and the processing parameters.
The usual way to develop a nanocomposite
structure is to make the alloys into amorphous and
then anneal them to crystallize them into the de-
sired microstructure [24,36]. The microstructure
obtained, however, is not very uniform and the size
of the soft phase tends to be too large for optimum
exchange coupling. Typical microstructure is
shown in Fig. 9a for a Pr Fe B melt-spun and
  
annealed sample. The average grain size estimated
from TEM micrographs is about 30 nm. But the
microstructure is not homogeneous and several
large a-Fe grains with size up to 50}100 nm can be
clearly seen (marked with arrows in Fig. 9a). In Fig. 9. (a) Typical microstructure of exchange coupled
nanocomposite Pr}Fe}B magnets, (b) e!ect of Nb Substitu-
order to obtain "ner a-Fe grains, additional substi- tions.
tutions M (M"Nb, Zr, Cr etc.) are often used to
hinder the grain growth of a-Fe during crystalliza-
tion [62,78]. As shown in Fig. 9b, a much "ner and with "ne a-Fe grains can be obtained after an
more homogeneous microstructure with an average appropriate annealing. As a result, the magnetic
grain size around 15}20 nm is obtained in Nb sub- properties, m , H and (BH) are improved as com-
 
stituted Pr (Fe Nb ) B samples without the pared to those of completely amorphous and an-
      
presence of large a-Fe grains [61,62]. As a result, nealed samples. Lower speed gives larger grains to
the coercivity increases from 4.9 kOe in Pr Fe B both 2 : 14 : 1 and a-Fe, while higher speed leads to
  
to 9.0 kOe in Pr (Fe Nb ) B . A similar ef- a partially amorphous structure that will result in
      
fect was reported in Zr substituted Pr Fe B a Pr Fe B/Fe structure with large a-Fe grains
    
magnets [79]. after crystallization annealing.
Another way to obtain "ner a-Fe grains is to Co substitution for Fe has also been studied
melt-spin the alloys at lower wheel speeds to get the extensively in nanocomposite magnets for improve-
"ne microstructure directly from the melt. For ment of their high-temperature properties. It is
R Fe B/Fe magnets [78] there is an optimum known that the Curie temperature of R Fe B is
   
wheel speed (about 16.7 m/s for Pr Fe B ) at signi"cantly increased with Co substitution while
  
which a uniform nanoscale R Fe B/Fe structure the anisotropy "eld is decreased [48]. From the
 
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391 381

Fig. 11. Crystallization behavior of R Fe Nb B ribbons as

   
seen by DSC.

squareness and magnetic properties of m "0.7


and H "6.5 kOe have been obtained in the

Pr ((Fe Co ) Nb ) B sample which has
Fig. 10. (a) E!ect of Co and (b) B substitution on the micro-  
 
 
 
  
a 50% Co substitution for Fe. On the other hand,
structure of Pr}Fe}Co}B magnets.
in Sm Fe C /Fe, Co substitution for Fe is found
  6
to signi"cantly reduce the size of the a-FeCo grains,
leading to a much smoother demagnetization curve
microstructural point of view, Co substitution leads and a higher m [64]. The high-temperature co-

to an increase of both the amount and the average ercivity is also signi"cantly improved by the Co
grain size of a-Fe (Fig. 10a) and the appearance of substitution due to the increase in Curie temper-
a small amount of R (Fe,Co) phase [62]. Thus ature, although the room-temperature coercivity in
 
the coercivity decreases with Co substitution, e.g., Co substituted samples is slightly lower due to the
from 9.0 kOe in Pr (Fe Nb ) B to 2.1 kOe decrease of the anisotropy "eld.
 
 
  
in Pr ((Fe Co ) Nb ) B . However, it is
 
 
 
 
  
further found that increasing the amount of B in 3.1.3. Crystallization behavior
Co-substituted samples helps to form a more ho- The crystallization behavior of a particular alloy
mogeneous and "ner overall microstructure system plays an important role in the microstruc-
and depress the formation of the undesirable ture development. Studies on the crystallization
R (Fe,Co) phases (Fig. 10b) [80]. As a result, the behavior of o!-stoichiometric alloys usually show
 
coercivity in Co substituted samples can be partly two or three peaks in the DSC and di!erential
recovered by increasing the B content. It is of inter- thermal analysis (DTA) curves (Fig. 11) [81], indic-
est to note that a smooth hysteresis loop with good ating that the transition from amorphous to the
382 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
"nal equilibrium crystalline phases takes place in
2}3 steps. For R Fe B/Fe type magnets, it is
 
found that a-Fe is crystallized "rst and there is
always a metastable intermediate phase formed be-
fore the "nal development of equilibrium R Fe B.
 
The metastable phase in the case of R"Nd or Pr is
characterized to have a BCC Y Fe B type struc-
  
ture and a Curie temperature of about 2003C [81].
For R Fe B/Fe with R"Tb or Dy and
 
Sm Fe C /Fe magnets, a metastable phase with
  6
TbCu (disorder hexagonal) structure appears be-

fore the "nal equilibrium 2 : 14 : 1 or 2 : 17 phases
are developed, respectively [81,82]. This indicates
that the annealing temperature must be high
enough to obtain the hard phase and the annealing
time should be as short as possible to minimize the
grain growth of the a-Fe. However, in most cases,
the grain size of the a-Fe is found still too large
even under the optimum annealing condition and
that additional substitutions like Nb, Zr, or Cr
have to be used to get "ner a-Fe grains as explained
before.
3.1.4. Magnetic hardening
The coercivity of hard magnets can be generally
written as [83]
H "(2K /k M )a !N M , (1)
!    )  
where K and M are the anisotropy and the satu-
 
ration magnetization of the material and a and
)
N are microstructure-dependent parameters

which describe the e!ect of the microstructure on
the crystal "eld and the local internal dipolar "eld.
The "rst term represents the modi"ed magnetoc-
rystalline "eld due to inhomogeneities (grain
boundaries, second phase, impurities, voids, dislo-
cations, etc.) in the real microstructure and the
second term the demagnetization "eld due to the
irregular shape of the grains.
The magnetization reversal process in nanocom-
posite magnets is more complicated due to the
coexistence of the hard and the soft phase which are
exchange coupled. The overall anisotropy constant
is reduced by the soft phase, which may be taken
into account by replacing a with a "a a where
) ) ) 
a is related to exchange coupling. Generally

speaking, the coercivity is controlled by the nuclea-
tion of the reversed domains in the soft phase. This
nucleation "eld would be very low if there was no
exchange coupling between the hard and the soft
phases. It is the exchange coupling that signi"-
cantly increases the nucleation "eld and thus
preserves a reasonable high coercivity. This e!ect is
known as &exchange hardening'. Several authors
have studied the magnetic hardening in nanocom-
posite magnets by using theoretical analysis [68,84]
or micromagnetic modeling simulations [75}77].
Kneller and Hawig [68] using a one-dimensional
model were able to qualitatively explain the greater
reversibility in the recoil curves. According to this
model the highest coercivity is achieved when the
size of the soft phase is twice the domain wall width
of the hard phase. Skomsky and Coey [84] have
used an analytical approach to predict the nuclea-
tion "eld and energy product in nanocomposite
magnets. According to their calculations the nu-
cleation "eld reaches a plateau when the diameter
of the soft inclusion in the hard matrix reaches the
Bloch wall width of the hard phase. Fischer et al.
[77] and Schre# et al. [85] have found by using
micromagnetic simulations that exchange interac-
tions between the phases suppress the nucleation of
reversed domains and thus preserve a high coerciv-
ity. They also predicted that M and H decrease
 
with increasing grain size and that the magnetic
properties are degraded by a non-uniform micro-
structure, which agrees well with the experimental
results [36,62,78,79]. All of these studies have
shown that the coercivity of nanocomposite mag-
nets depends strongly on the anisotropy "eld of the
hard phases and on the grain size of the soft phase
which should be of the order of the domain wall
width of the hard phase.
3.2. Precipitation hardened 2 : 17 magnets
These magnets consist of a "ne mixture of 1 : 5
and 2 : 17 [86] phases. SmCo has a hexagonal

structure with a"0.5 nm and c"0.4 nm. Many of
the other intermetallic compounds can be derived
from the 1 : 5 by replacing a fraction of rare earth
atoms with a pair of transition metals (known as
dumb bells) [87]. The Sm Co structure with
 
a"0.840 nm and c"1.217 nm is obtained by the
replacement of one-third of the Sm atoms with
a pair of Co atoms. Whether the rhombohedral or
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391 383

Table 3
Magnetic properties of commercial magnets

Magnet Alnico 5}7 Alnico 9 Cast Ferrite RCo R T R T B

    
B (G) 13 500 10 600 4100 9500 10 900 12 000

H (kOe) 0.75 1.55 2.9 15 7 '12

(BH) (MGOe) 7.5 9.2 4 22 28 35

¹  (3C) 520 520 400 250 300 150

!a (%/3C) 0.02 0.02 0.2 0.045 0.030 0.1
!b (%/3C) 0.27 0.40 0.2 0.60
¹ (3C) 900 860 450 700 800 310


hexagonal modi"cation of 2 : 17 is obtained de-
pends on whether this replacement occurs such that
the resulting stacking sequence is of the AB-
CABC2or ABAB2type, respectively.
Rare earth cobalt permanent magnets have large
energy products, which originate from their high
magnetocrystalline anisotropy [88] which is pre-
dominately due to the rare earth sublattice, because
of the non-uniform charge distribution in the 4f
shell. In the SmCo magnet, the anisotropy "eld

exceeds 300 kOe and the coercivities produced are
greater than 30 kOe. However, its lower magnetiz-
ation limits the energy product to only 25 MGOe
(Table 3). The anisotropy "elds are weaker in
Sm Co , but its higher magnetization leads to
 
higher energy products above 30 MGOe.
The development of 2 : 17 permanent magnets
was the result of intense research in the late 1960s
and 1970s. It was "rst found that partial substitu-
tion of Co with Cu causes the formation of precipi-
tates [89], which were found to pin the domain
walls and lead to high H (precipitation hardening).

Other studies [90] showed that the magnetization
can be further increased by partial substitution of
Co with Fe, which also stabilizes the c-axis anisot-
ropy. (This substitution is possible in the 2 : 17
system but not in the 1 : 5 system because the
SmFe phase does not exist.) However, at higher
 8
concentrations, Fe (which substitutes at the dumb
bell sites) tends to destabilize the 2 : 17 structure
upon cooling through the Curie temperature be-
cause of strong negative exchange interactions [91]
(due to the small Fe}Fe spacing at the dumb bell
sites), and this leads to the formation of soft Fe}Co
phases [92]. In 1977, Ojima et al. [93] made the
important discovery that additional small substitu-
tions of Co with Zr (or Hf [94], Ti) allow a greater
Fe content in the magnet without the formation of
Fe}Co phases, leading to energy products (BH)
exceeding 30 MGOe in o!-stoichiometric
Sm(Co,Fe,Cu,Zr) magnets with 6.8)Z)7.4 re-
8
ferred to as R T in Table 3.
 
3.2.1. Magnetic properties
The 2 : 17 precipitation hardened magnets have
an initial magnetization curve which is distinctly
di!erent from those of other magnets [40]. The
virgin curve of low H magnets is typical of &uni-

form domain wall pinning' (inside the grains) with
the magnetization slowly increasing until a critical
"eld (which is close to H ) beyond which it drasti-

cally increases to saturation (Fig. 12). The virgin
curve of higher H magnets shows a larger increase

at low "elds but not as much as that observed in
SmCo and Nd Fe B magnets. This behavior in-
  
dicates a non-uniform domain wall pinning with an
additional contribution from localized pinning at
grain boundaries.
Our latest studies [95,96] on the development of
magnets with high operating temperatures showed
that large coercivities can be obtained in
Sm(Co,Fe,Cu,Zr) over a range of Z values from
Z"5.5}9.1. The best high temperature properties
are obtained on the lower Z magnets as shown in
Fig. 13. The temperature dependence of coercivity
is also found to be very sensitive on the amount of
Cu in the magnet and on the size of cellular micro-
structure.
384 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
Fig. 12. Initial magnetization curves and "eld dependence of
coerecivity in nucleation and pinning-type magnets.
Fig. 13. Temperature dependence of coercivity
Sm(Co,Fe,Cu,Zr) magnets with di!erent Z.
8
3.2.2. Microstructure * magnetic domains
The hard magnetic properties of the precipita-
tion-hardened 2 : 17 magnets can be achieved only
[40] through a series of complex heat treatments.
The sintered samples are "rst solution heat-treated
at &12003C and then quenched to room temper-
ature. The high coercivities are developed after an
aging heat treatment in the temperature range of
800}8503C followed by a slow cooling to 4003C (or
step aging to 4003C) and then quenching to room
temperature. Transmission electron microscope
studies [13,97}100] reveal a "ne cellular micro-
structure in the 2 : 17 magnets with lower co-
Fig. 14. Cellular microstructure in 2 : 17 magnets.
in
Fig. 15. Superposition of cellular and lamellar microstructure.
ercivity. The cells (&50 nm) have the 2 : 17
rhombohedral structure, and they are surrounded
by thin (4}10 nm) coherent walls with the 1 : 5
hexagonal structure. In the higher coercivity 2 : 17
magnets [13], the cells are apparently much coarser
(&100 nm) (Fig. 14), and thin lamellae (&3.0 nm)
are superimposed on the cellular microstructure
(Fig. 15). According to Rabenberg [101], the lamel-
lae have the 1 : 3 rare earth structure and lie along
(0 0 0 1) planes. On the other hand, Fidler et al.
[102] claimed a 2 : 17 hexagonal structure for the
lamellae. The cell boundaries are found to be rich
in Cu while Zr concentrates in the thin lamellae
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391 385

Fig. 16. Room temperature hysteresis loops at di!erent aging

temperature in a commercial 2 : 17 magnet.
Fig. 17. Magnetic domains in 2 : 17 magnets.

(referred to as the Z-phase). The 2 : 17 rhombohed-

ral cells are enriched in Fe. The cellular and lamel-
lar microstructures develop during the&800}8503C
heat treatment and do not change in the sub-
sequent cooling [103]. This is in contrast to the
magnetic properties, which change drastically dur-
ing the latter heat treatment (Fig. 16). However,
energy-dispersive X-ray analysis (EDS) studies sug-
gested a di!usion of the various elements during
cooling with an increase in the Cu content of the
cell boundaries. Such an increase in Cu causes
a dilution of the magnetic properties of the 1 : 5
phase and leads to domain wall pinning at the cell
boundary [104].
Lorentz microscope studies [99] show the pres-
ence of magnetic domains which appear to be
smaller (4000 As wide) in the higher H materials

and are not a!ected by the presence of lamellae
(Fig. 17). The wavy nature of the domain walls does
not change after the application of a magnetic "eld,
indicating that they are pinned at the 1 : 5 cell
boundaries.
Our latest studies on high temperature 2 : 17
magnets showed that the microstructure is very
sensitive on both the Z value and the amount of Cu
on the magnet. Lower Z values and higher amounts
of Cu lead to a much "ner microstructure as shown
in Fig. 18. This microstructure causes a smaller
temperature dependence of coercivity provided the
right amount of Cu is used. In fact, Cu controls Fig. 18. E!ect of Cu content on cellular microstructure in sam-
both the magnitude and temperature dependence ples with Z"7.0.
386 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
of coercivity, from large negative b (b"dH /d¹) to

a much smaller negative b to a positive b [95]. This
behavior can be explained by the fact that Cu is
concentrated on the SmCo Cu cell boundaries
\6 6
thus in#uencing the magnetic properties of the 1 : 5
phase, which then interacts strongly with the do-
main walls to lead to the observed high coercivity.
3.2.3. Magnetic hardening
A number of magnetic hardening models have
been proposed to explain the coercivity of these
magnets. A rough estimate of the coercivity can be
obtained by considering the gradient in domain
wall energy that exists across the cell boundaries
using the expression [105] H "(1/2M ) *c /d
   
where d is the domain wall thickness and *c the
 
di!erence in domain wall energy across the cell
boundary. Fidler et al. [106] used a di!erent ap-
proach taking into account the magnetoelastic
coupling energy between magnetostrictive stresses
of domain walls and lattice deformation strains and
obtained good agreement with the observed co-
ercivities. Paul [107] has treated the case of a 1803
domain wall interacting with planar defect and
explained the observed coercivity in these magnets
as a function of defect size and the intrinsic proper-
ties (A, K, M ) of the matrix and defect.

Monte Carlo simulations [109] were recently
performed on a simpli"ed model for the 2 : 17 mag-
nets to understand how the domain walls are de-
pinned by a "eld at high temperatures. For large
"elds, the domain walls are depinned from the cell
boundaries. The depinning process begins with
a kink occurring in the wall at the corner where the
horizontal domain walls intersect the grain bound-
aries. Physically, this idea is very reasonable. If one
wants to move a carpet across a room, it is easier to
create a rumple (corresponding to the kink) in the
carpet and move the rumple across the room. This
suggests that if the grains are longer, or if the
corners are eliminated, the coercivity will be in-
creased.
3.3. Granular xlms with high anisotropy materials
The drive for higher magnetic recording density
with a low system noise impose the need for a me-
dium consisting of magnetically isolated grains
with size below 10 nm [110}112]. This size is close
to the superparamagnetic limit of existing materials
which makes them unsuitable for this application.
Therefore, materials with high magnetocrystalline
anisotropy are needed to avoid thermal #uctu-
ations and demagnetizing "elds that tend to de-
stabilize the magnetization of the recorded bits
[106}108]. Current studies have been focused on
nanocrystalline rare earth compounds [5,26] and
CoPt and FePt [27,28] because of their high an-
isotropy which are expected to have coercivities
greater than 2 kOe. We have recently started a pro-
gram to obtain nanocomposite X/> "lms consist-
ing of magnetically hard nanoparticles of X"
CoPt (FePt), rare earth intermetallic compounds,
in a non-magnetic matrix >"Ag, C, W.
The granular structure is obtained by "rst de-
positing X/> "lms in a multilayer form (consisting
of 100 repetitions) and subsequently annealing the
samples in the temperature range of 500}8003C to
form the desired phase as nanophase particles. The
"lms were prepared by magnetron sputtering de-
position from two 2 targets of X and >. The base
pressure of the chamber was 3;10\ Torr and
high purity Ar was used for deposition at ambient
temperature with a pressure of 5 mTorr. In this
section we present some preliminary results on
these materials.
3.3.1. CoPt}FePt nanoparticles in Ag(C) matrices
Co}Pt and Fe}Pt alloys with composition close
to equiatomic have been studied extensively in the
past, as possible candidates for permanent magnets
[113,114], because of the large value of magnetoc-
rystalline anisotropy of the ordered face centered
tetragonal (FCT) phase, resulting in coercivities
greater than 5 kOe. These alloys usually undergo
a phase transformation at below 8003C from a dis-
ordered face centered cubic (FCC) phase at high
temperatures to the ordered FCT phase at lower
temperatures. Recently FePt and CoPt "lms have
received considerable attention for magnetic re-
cording and magneto-optical recording applica-
tions [27]. Granular CoPt/C "lms consisting of
Co-rich hexagonal Co}Pt particles in a C matrix
have been reported by Delaunay et al. [115].
However, the "lms had a low coercivity because of
the lower anisotropy of the hexagonal Co-rich
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391 387

Fig. 19. Development of coercivity with annealing temperature

and time in CoPt/Ag.

phase. We have recently prepared nanocomposite

CoPt/Ag(C) and FePt/Ag(C) "lms consisting of the
highly anisotropic tetragonal CoPt (FePt) phase
with coercivities in the range of 2}9 kOe [28].
All the as-deposited "lms are magnetically soft
with H (100 Oe. Upon annealing and subsequent

transformation to the FCT structure, the samples Fig. 20. Typical hysteresis loops in CoPt/C samples aged at
become magnetically hard (Fig. 19). In the initial di!erent temperatures and times.
stages of ordering the coercivity is a few hundred
Oe but it increases drastically with subsequent an-
nealing reaching values beyond 15 kOe. The max-
imum value was found to depend on the layer
thickness with the highest value (17 kOe) obtained
in thicker layer samples (t "2 nm/t "2 nm)
 
(Fig. 19). Also the optimum annealing times are
much shorter at higher annealing temperatures as
expected. Fig. 20 shows typical hysteresis loops
obtained on a sample annealed at di!erent temper-
atures. Prolonged annealing leads to the develop-
ment of a shoulder in the demagnetization curve.
Values of reduced remanence, m found from the

hysteresis loop data (with values of M determined

from the law of approach to saturation) are in the
range 0.62}0.85 with the larger values obtained in
Fig. 21. Typical microstructures in CoPt/C samples.
underaged samples. Transmission electron micro-
scope studies showed face centered tetragonal
(FCT) CoPt nanoparticles embedded in a Ag (car- For most of the samples studied the size of the
bon) matrix (Fig. 21). The size of the particles in- CoPt particles is well below the single domain size
creases from 5 nm in the as-made state to 7}12 nm of the FCT-CoPt phase which is around 0.6 lm,
in the optimally annealed state. so magnetization reversal should be based on a
388 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391

coherent rotation mechanism. For coherent rota-

tion in an assembly of randomly distributed non-
interacting particles with uniaxial anisotropy K the
coercivity is given by H "0.96K/M [29]. This
 
would lead to an H &80 kOe if the bulk value of

K&4.9;10 erg/cm is used. The values of the
measured coercivity are smaller by one order of
magnitude. This large discrepancy may be due to
several factors. One could attribute this to the size
dependence of coercivity, which for an assembly of
randomly orientated non-interacting particles will
be [116]

 
0.96K <  
H" 1!  , (2)
 M <
 Fig. 22. Typical microstructure in SmCo /W "lms.

where < is the critical volume for superparamag-

netism, estimated by K< "25k¹. The bulk value
 from 5 to 35 nm for both. The total "lm thickness
K gives a volume as small as < "21 nm which
 was kept around 1 lm. All "lms were covered by
corresponds to a particle size of 2.5 nm. The TEM
studies show a particle size in the range 7}26 nm a 100 nm layer of = for protection.
which would account only for a reduction of co- Magnetic measurements on the as-made "lms
ercivity around 20%. Another possibility for the showed an amorphous-type behavior. The coerciv-
explanation of this discrepancy is the consideration ity, at room temperature, did not exceed 50 Oe. The
of the interaction e!ects, which are expected to lead "lms were annealed at various temperatures
to remanence enhancement accompanied by reduc- ranging from 500 to 9003C at di!erent annealing
tion of the coercivity [117]. However, for interac- times (5}50 min) in a vacuum with base pressure
tions related to m "0.78 the expected reduction of better than 1;10\ Torr. This process resulted in the
 breaking of the multilayer structure and led to nano-
coercivity is around 10% [118]. Therefore, interac-
tion e!ects cannot explain the large di!erence that particles of magnetically hard SmCo (Nd Fe B)
  
is observed even in samples with isolated grains. phases embedded in a = matrix (Fig. 22).
The large discrepancy may be related to the fact Preliminary results show that at low annealing
that for the relatively short annealing times which temperatures (up to 6003C) the hysteresis loop was
are used to optimize the microstructure, the order- quite square with coercivities between 1 and 6 kOe
ing of the FCT phase is not complete. The splitting (Fig. 23). At higher annealing temperatures
of the (0 0 2)}(2 0 0) re#ections in the XRD patterns ('7003C) a shoulder appears on the demagnetizing
corresponds to a ratio c/a"0.99 compared to the curve which may be due to the development of
bulk value of c/a"0.97 and consequently anisot- a second soft phase. For these "lms typical values of
ropy is expected to be lower than that of the bulk H were between 10 and 20 kOe for these "lms.

value. Furthermore a reduced K would give a lower
< and lead to an enhanced size dependence ac-

cording to Eq. (2). 4. Projections

3.3.2. SmCo5(Nd2Fe14B) nanoparticles in a W matrix Research in nanophase hard magnetic materials

The "lms were deposited onto (1 0 0)Si wafers,
with a naturally grown oxide layer on the surface, in
a multilayer form consisting of SmCo (Nd Fe B)
  
and = layers. The bilayer thickness was varied
is expected to continue with greater intensity due to
their importance in science and technology. From
the fundamental point of view, research will be
focused on size and surface/interface e!ects in
 G.C. Hadjipanayis / Journal of Magnetism and Magnetic Materials 200 (1999) 373}391
Fig. 23. Typical hysteresis loop of SmCo /W thin "lm after

annealing.
isolated and compacted nanoparticles/nanograins
of materials with high anisotropy, including the
rare earth intermetallic compounds. In such
nanoparticles (nanograins), the surface atoms con-
stitute most of the particles and the broken sym-
metry at the surface and di!erence in bonding and
exchange interactions are expected to have dra-
matic e!ects on the intrinsic magnetic properties
including the saturation magnetization, magnetic
anisotropy, and Curie temperature. The hysteresis
behavior of such particles will also be of import-
ance including their superparamagnetic and mag-
netic after e!ect behavior. The high anisotropy
nanoparticles can be used to check the validity of
the proposed time independent quantum tunneling
mode of magnetic after e!ect. The critical temper-
ature ¹ of transition from the thermal activation

to the quantum mechanical magnetic viscosity
mode is believed to be related to the anisotropy
"eld of the material. Because of the large range of
anisotropies in intermetallic compounds, a large
e!ect is expected on ¹ .

From the technological point of view, the focus
will be on materials consisting of anisotropic
nanoparticles embedded in a non-magnetic matrix
for ultrahigh magnetic recording density media.
E!orts should be directed at optimizing the micro-
structure with uniformity in particle size and regu-
lar arrangement in space.
389
In nanocomposite materials, e!orts should be
directed at optimizing the microstructure and ob-
taining a "ne and uniform distribution of exchange
coupled soft and hard phases with a smaller size in
the soft phase. Also, for future applications, one
needs to obtain this microstructure in bulk. The
mechanical properties of nanophase magnets are
also expected to be much better than those of
classical sintered magnets which are very brittle.
However, new processing techniques must be found
to develop bulk anisotropic magnets with the
nanograin structure.
Acknowledgements
Work supported by MURI, DOE and NSF.
I would like to thank Dr. Zhongmin Chen and Joe
C. Christodoulides for their help in this article and
Dr. Niarchos's group at &Demokritos' National Re-
search Lab in Athens, Greece for their collabora-
tion on CoPt/Ag(C) "lms.
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