IEEE TRANSACTIONS ON MAGNETICS, VOL. MAG-13, NO.

2 , MARCH 1977 953

Magnetic Anneal Anisotropyin Amorphous Alloys

FRED E. LUBORSKY, SENIOR MEMBER, IEEE, AND JOHN L. WALTER

Abstract-The uniaxial magnetic anisotropyKu induced by a magnetic sults, such as those on Ni-Fe [ 6 ] ,cannot be compared quanti-
anneal hasbeendetermined,afterstressrelief,foraseries of alloys
tatively with the theory because of the finite coolingrate used.
given by (FeyNi1&0B20.Forall of these alloys K , depends on
anneal temperature as predicted by directional order theory. The con-
The use ofsuchcooling rates wasnecessary to preventthe
formationofthe Ni,Fe superlattice. The amorphous alloys
centration dependence of K , in these alloys is also consistent with di-
rectional order theory.Themaximum K,, correctedfor its tempera- provide us with a unique opportunity to compare K , t o the
ture dependence, occurs at the compositiony = 0.5. However, K,, does theoretical predictions for awide range of compositions.
not fall to zero at y = 1 as predicted if directional order is assumed toTheas-cast amorphous alloys are structurally unstable and
arise only from Fe-Ni pairordering.Theseresultsareinterpretedas
must,therefore, be annealed to relax thestructurewithout
suggesting a role of the glass former, boron, in the directional ordering,
perhapsasan"interstitial."Theinteractionenergyderivedfrom causing crystallization. After this treatment it is hoped that
the
subsequentanneals
results is negative as expected for interactions leading to precipitation. to produce directional order will not
Its largevalue of =-7.5 X ergscorresponds to acriticaltempera-
change the structure further. This has been found to be true
ture for precipitationof 3000 K. [l], 121. The amorphous alloys arealso in metastableequi-
librium with respectto crystallization but the directional order-
INTRODUCTION ing anneals can be carried out at sufficiently low temperatures
compared to the temperatures required for crystallization that
M AGNETIC annealing to produce directional order in
amorphous metallic alloys was recentlyreportedfor
the alloys Fe,5P,5Clo [ l ] , Fe40Ni40P14B6[2], andforthe
the system can be assumed to be "stable."
In the following we report on the magnetic anisotropy in-
duced by magnetic annealing in the series of alloys with nom-
nearlyzeromagnetostrictive alloy (Feo.04Coo.96)75P16B6A13
inal compositions (in at. %) (FeyNil-y)80BZ0. These results
[ 3 ] . By analogy to the related crystalline alloys, and from
are thencompared to thepredictionsof directional order
studies of the kinetics of reorientation of the induced aniso-
theory.
tropy [4], it was suggested that the induced anisotropy K , in
these amorphous alloys was developed bybasically the same METHODS AND RESULTS
mechanismasin the crystalline alloys; namelypair ordering.
Ribbons of amorphous alloys were prepared by quenching a
Pair ordering predicts that K , = 0 if there is only a single type
molten stream of the appropriate alloy onto the surface of a
of magnetic atom, as in the Fe75P15C10alloy, assuming only
rapidly spinning drum, essentially as recently described [7] in
the magnetic atoms are involved. Thus it is apparent that in
these alloys we see contributions to K , from either monatomic some detail. The ribbons were all -25 pm thick and -1mm
directional order analogous to interstitial or vacancy ordering wide. All samples were tested in various ways to be sure that
in crystalline alloys, or from pair ordering of a single magnetic they were amorphous: crystallization temperatures were de-
speciesin an inhomogeneousenvironmentofnonmagnetic termined using a differential scanning calorimeter (DSC) and
atoms. from changes in coercive force and remanence; heatsof crystal-
Directional order theory [5] predicts the dependence of K , lization werealso determinedfromthe DSC scans; andthe
onannealtemperature,magnetizationattheannealingand samples were bent to be sure that they were ductile; the ab-
measuring temperature, and on composition. In thecrystalline sence of long-range crystalline order was confirmed by X-ray
alloys in the Fe-Co-Ni system complications arise in compar- diffraction for some of the alloys. The temperature required
ing experimental results to the theory because thermodyn&ic for stress-relief, during a 2-h heat-treatment, was determined
equilibrium of the ordering species cannot be achieved before for each alloy, by measuring the relaxation of a coiledhoop as
competing reactions start. These competing reactions may be described previously [2]. All of the alloys used in this work
the development of long-range order, i.e., superlattice forma- were completely stress-relieved on heating at 325°C for 2 h.
tion or of segregation into two phases.The reported results The maximum anisotropy induced bymagneticannealing
appear t o depend sensitively on the details of heat treatment was determined as follows. A 10-cm length of each alloy was
and the agreement between different investigators is not :good. sealed in vacuum in a small diameter pyrex tube. Each alloy
Two general results are common: K , vanishes as the concen- was annealed at 325°C for 2 h in a field of -30 Oe directed
tration of solute becomes small, and it vanishes at composi- along the long axis of the ribbon. This provided the stress-
tions and heat treatments which produce complete long-range relief and, for these samples with Curie temperatures above
order. It should be noted that much of the experimental re- 325"C, provided the first magnetic anneal. Each sample was
then cooled rapidly to room temperature (-6O"/min) with the
field on, and its dc hysteresis loop measured to determine its
Manuscript received August 26, 1976; revised October 26, 1976. This initial susceptibility, XII. For a material with infinite perme-
work was partially supported by the Office of Naval Research.
The authors are with General Electric Company, CorporateResearch ability l/xll = N , thedemagnetizing factor.A new sample
and Development, Schenectady, NY 12301. was then prepared and annealed in a field of -3500 Oe di-
 954 IEEE TRANSACTIONS ON MAGNETICS, MARCH 1911

rected across the width of the ribbon giving the susceptibility

I
after a transverse anneal, X I . The induced anisotropy field is 6 X IO3
then P I ,

= M , [ ( 1 IHx ,d - (1lXIl)l (1 1
and K , = MsHu/2. The transverse anneals were repeated iso-
thermallyuntil a constant H , was obtained at each anneal
temperature. The results for H , as a function of time of anneal 2
are shown in Fig. 1 . The equilibrium value of H , at the lowest
temperature, 226"C, was obtained by a linear l / t extrapolation
to t = co. This increased H , by an average of 3.6 t 0.8 percent 01 I 1 I I I I I I
0.2 0.4 0.6 0.8 I.o
over the value at the last anneal time. As noted previously [ 2 ] , y=ATOMIC FRACTION OF IRON
isinsensitive to changes in inducedanisotropy along the
Fig. 2. Maximum induced anisotropy as function of' iron content of
long axis.Thiswas confirmed for a number of alloys in the amorphous Fe-Ni-B alloys annealed at different temperatures.
present work. For only one of the samples, namely Fe80B,o,
the susceptibility method of obtaining H , could not be used TEMPERATURE, K
because the M-H curves were not linear over the major frac- i$O.-- 2?0 300 400 500 600
tion of their magnetization. For these, we measured the area
enclosed between the magnetization curveof the sample an-
nealed in the parallelfield andthe sample annealed inthe
transverse field. This gave the same value of H , when used on
the othersamples where the B-H curve is linear.
After the lowest temperature anneal, the samples were then
annealed at increasing instead of decreasing temperatures. The
values of H , were an average of only 3.7 percent higher; rang-
ing from - 1.5 to 7.1 percent. We conclude from this that the
equilibrium values of H , can be achieved essentially reversibly
with either increasing or decreasing temperatures of anneal.
The maximum inducedanisotropyobtainedfrom the first
sequence of anneals at decreasing temperatures for these alloys TEMPERATURE, "C
is shown in Fig. 2. An analysis of the behavior of their Curie Fig. 3. Saturation magnetization versus measurement temperature for
temperaturesandsaturationmagnetization as a function of Fe-Ni-€3 amorphous alloys.
composition are reported separately [8] but their magnetiza-
tion as a function of temperatureis shown in Fig. 3 . The solid loop measurements on toroids, or long straight samples, in
portions of the curves with no data points were measured with maximum fields of 50 Oe. A l / H extrapolation was then used
a recording force balance using a 1-cm long ribbonin a 250-0e to obtain M,, The dashed portion of the curves are extrapola-
field along its long axis. A heatingrate of 20 deg/min was tions based on normalizing all the curves to the same MS/Ms,,
used. The datapoints shownwere obtained from hysteresis- versus T/T, reduced curve. Note the M , versus T curves for
two of the alloys indicate that crystallization started before
reaching their Curie temperatures. All of the reduced mag-
netization curves showed a negative deviation at low tempera-
tures and a small positive deviation at high temperatures com-
pared to the curve calculated from molecular field theory for
S = 1/2. These deviations are approximately the sameas ob-
served for Fe, Ni, and Co.

0.5C THEORYVERSUS EXPERIMENT: THEORY

Directional order theory [5] predicts that at equilibrium

Ku = A ~ ( ~ ) W T / M O ) ' (/Mo)'/le
MO (2)
assuming that the pair energy is pseudodipolar where A is a
I( oo y - c - - - + - + . . .-+-2 +
,.+
.. constant which depends on the atomic arrangement and the
. _ - -range of interactions
I considered,
- f-
( c ) is a function which de-
IO 100
TIME, hours
pends on the concentrations of the ordering species as will be
Fig. 1. Developmentofinduced anisotropy field for Fe-Ni-B amor- described below, and M o ,M T , and M o are the magnetizations
phous alloys at decreasing anneal temperatures. at the anneal temperature 0 , and at the measuring tempera-
LUBORSKY AND WALTER:
ANNEAL MAGNETIC ANISOTROPY 955

tures, T, and OK, respectively. For very dilute solutions for RESULTSFOR Fe-Ni-B
monatomic directional, order f ( c ) = c, the concentration of The experimental values of K , for the Fe-Ni-B alloys shown
the ordering species. Fordiatomic directional, order f ( c ) = in Fig. 2 have been replotted in Fig. 4 to factor out the anneal
Ci where C, is the concentration of thedilute species. and measurement temperatures using the function KL = K,B/
If neither constituent is dilute, only approximate expressions (Mo ( M T / M , ) ~obtainedfrom (2). This. should depend
are available. For the case in which the nonmagnetic interac- only on the concentration function assuming A is independent
tion energy approaches zero, i.e., for ideal solutions, so that of temperature and composition. Some points to note are as
only a single disordered phase exists, then follows. 1) KL appears to peak at y = 0.5 as predicted theo-
retically. 2) The various anneal temperatures yield the same
value of KL at eachy as predicted. 3) The values of KL at y =
where N is the number of atoms per unit volume, C, and C, 1 are not zero as predicted by theory for the assumption used
are the relative fractions of a and b atoms, andn is the number here of pair ordering of the magnetic atoms. 4) The best fit
of possible orientations of each pair in a crystal lattice. For of the data to Iwata's theoretical curves is for kT/2V = -0.4
nonideal solutions, the effective nonmagnetic interaction ignoring the deviation at y = 1 for the moment. The only re-
energy V between like pairs i s important. NBel[5] has shown sults previously reported [ 111 on crystalline Ni-Fe alloys which
that for aweak interaction energy have beencompared to theory [ l o ] , [ 121give a value of
2NnCi C; exp (- V/kO) kT/2V = 0.3 to 0.6, i.e., a positive interaction energy,leading
f(c) = (1 + X ) q 1 t (1 + x ) 1 / 2 ] 2 (4) to superlattice formation, as is
observed fromlong-time
anneals. The negative V found for the amorphous alloys sug-
where gests that segregation into two phases,orprecipitation will
occur, as is observed. For the anneal temperatures of 499 to
x = 4C,Cb[exp (- Vlke) - 11.
598 K the interaction energyis calculated to be - 0.85 X
For ideal solutions, V = 0 and (4) reduces to (3). When IVI is to - 1.O X ergs. We can nowestimatethe critical tem-
large, long-range ordering may take place at the anneal tem- perature for precipitation Tp. We consider the amorphous
perature. When V > 0 the systems tends towards superlattice alloys as a close packed structure with a coordination number
formation; when V < 0 there is a tendency towards precipita- 2 = 12; veryclose to the value calculatedfromstructural
tion. Thus in amorphous alloys where superlattice formation analysis [ 131. From the analysis by Guggenheim [ 141 for the
is not possible because of the absence of long-range structural close-packed structure for precipitation-type alloys using his
order, and because we do observe precipitation, we expect to quadruplet approximation and
consideringonly
nearest
always find V < 0. In these cases, (3) or (4) are no longer neighbors for the composition y = 0.5
valid. The effects of large IVI were calculatedbyIwatafor Tp = w/2.23k (5)
bcc [9] and fcc [ 101 alloys. We use here the results calculated
byIwatafor fcc alloys above their critical temperature for where w is the interchange energy for a and b atoms and k is
precipitation since this approximates the close packed amor- Boltzmann's constant. The interaction energy V = w / z and
phous structure. These are shown in Fig. 4 normalized to K , (6) = T, = 2.69(2V/k).
5700 erg/cm3 at y = 0.5. The ideal solution, i.e., V = 0 con-
centration dependence from (3) is also plotted. Iwatareported Thus at 598 K, T p = 3900 K. Such a high value of Tp was also
results for kT/2Vonly to - 0.6; thecurve at - 0.4 was obtained calculated for crystalline Ni-Co alloys [ l o ] , [ 121. It was at-
by a shortgraphical extrapolation ofhis calculations. tributed to the assumption in the theoretical analysis that the
temperature dependence of the ordering energy was propor-
tional to the square of the Brillouin function. Thishas not
beenexperimentally verified forthese Fe-Ni-B amorphous
6X alloys. In an amorphous Fe-Ni-P-B alloy K , was reported to
be proportional to both M 2 [ 151 and to M 3 * 7[4]. In a range
ofcompositionsof crystalline Fe-Ni films, K , was propor-
tional toM3.6 [16].
The nonzero value of K , at y = 1 suggests a magnetic order-
ing contribution from a source other than the conventional
transition metalatom pairs justconsidered. We suggest this
source is associated with the glass-forming atom, boron. The
boron may act in a similar manner t o the way interstitials act
0
in developing directional ordering in crystalline materials. The
0.2 0.4 0.6 0.8 I.o existence of interstitial ordering was also suggested [ 171 as the
y=ATOMICFRACTION OF IRON
origin of thedifference in activation energymeasured for
Fig. 4. Maximum induced anisotropy corrected for anneal temperature stress-induced ordering versus magnetic induced ordering. An
and magnetization for Fe-Ni-B alloys. Curves are from calculations
for directional order by Iwata, normalized to give best fit to these alternative ordering mechanism may exist whereby iron atom
data. pairs may develop orderin the Fe-B matrix.
956 TRANSACTIONS IEEE MARCH ON MAGNETICS, 1977

6 I I I I I I I CONCLUSIONS
- The magnetically inducedanisotropyin(FeyNi,-y)B20 al-
loys follows closely thedependence on anneal temperature
-- 4 predicted by directional order theory. The concentration de-
%
I
- iFeyNi,-y)soB,o pendence can be fit tononideal
directional
for
theory
order
2
I
- 3
Y
solid solutions of Fe-Ni. The peak value of K , ,corrected for
2- “C temperature, does occur at y = 0.5, as predicted. However,
0 325
0 300 there is an unexplained
anisotropy a t y = 1 amounting to -25
- 0 260
v 226 percent of the peak K,. This suggests either interstitial type
0.
0.2
I I
0.4
ordering of the boron with respect to the local Fe order, or
y=ATOMIC
FRACTION OF IRON Fe pair ordering
with
respect tomatrix
a of Fe-B. The nega-
~ k5..~~~i~~~ induced anisotIopy corrected as in ~ i 4 and
~ .now tive interaction energy is of the type leading to precipitation
subtracting value at y = 1. Calculated curves arerenormalized to as expected,incontrast to the positive interaction energy
give best fit to these results. found for crystalline Fe-Ni alloys.

ANNEALTEMPERATURE, K ACKNOWLEDGMENT
500 600 700 800
8 x lo3, I I I I The authors appreciate the able assistanceof W. Rollins in
- preparing the ribbon samples and B. J. Drummond in carry-
ing out the magnetic measurementsand calculations.
0 0.563
0 0.625 REFERENCES
v 0.75 -
A 0.875
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[4] F. E. Luborsky, AIP Conference Proc. No. 29,209-210 (1976).
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ANNEAL
TEMPERATURE, ‘C Magnetism and Metallurgy, Editedby A.E. Berkowitz and E.
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Fig. 6. Inducedanisotropy as functionof anneal temperature for
[6] S. Chikazumi and T. Oomura, J. Physical SOC.of Japan, 10,842-
Fe-Ni-B alloys. Solid lines are calculated for directional order nor-
849 (1955).
malized to give best fit to data at
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the best fit again. The best fit corresponds now to kT/2V = 29,252 (1958).
-0.5 giving V = -0.69 X to
-0.83 X ergs for
the [ 121 M. Yamamoto, S. Tanaguchi, and K. Aoyagi, Sci. Repts. Research
Insts. Tohoku Univ.,A13, 117 (1961).
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the temperature dependence in (2), normalized to obtain the 220-221 (1975).
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(1970).
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