Rf-Mössbauer study of the magnetic
properties of nanocrystalline
FeNiZrB and FeNiCoZrB alloys
M. Kopcewicz and T. Kulik a)
Institute of Electronic Materials Technology,
01-919 Warszawa, Wólczyńska Street 133, Poland,
a)
Faculty of Materials Science and Engineering,
Warsaw University of Technology,
02-507 Warszawa, Wołoska Street 141, Poland,
Introduction
Nanocrystalline alloys are excellent soft magnetic materials
with wide practical applications [1].
The main disadvantage: high brittleness.
FeNiZrB alloy: show improved mechanical properties but at the
expense of saturation magnetization of nanograins [2].
In order to increase the magnetization - Co is added.
Aim of the current study:
Investigation of magnetic properties of the nanocrystalline alloys:
Fe31Ni50Zr7B12 (Co-free alloy) and Fe41Ni40-xCoxZr7B12 (x=10, 20)
(Co10 and Co20 alloys) by means of the rf-Mössbauer technique.
This technique permits us to study changes of magnetic
anisotropy and to follow the variations of magnetostriction
associated with the formation of nanocrystalline grains.
Experimental procedure
Samples:
amorphous alloys Fe31Ni50Zr7B12 (Co-free alloy),
Fe41Ni30Co10Zr7B12 (Co10 alloy),
and Fe41Ni20Co20Zr7B12 (Co20 alloy),
prepared by the melt quenching technique.
The ribbons: 3 to 5 mm wide and about 25 m thick.
The nanocrystalline alloys: formed by 1 hour annealing in vacuum of amorphous
precursors (annealing temperatures: Ta= 440 –770oC).
The rf-Mössbauer measurements: performed during sample exposure to a radio
frequency (rf) magnetic field with a frequency of 61 MHz, and the intensity of
which was varied between 0 and 20 Oe.
The rf field was applied in the plane of the sample.
The rf-Mössbauer investigations were accompanied by measurements of quasistatic hysteresis loops.
Rf-Mössbauer technique
combines the Mössbauer effect with phenomena
induced by an external radio-frequency magnetic
field in ferromagnetic materials (see e.g., [3, 4, 5]).
Effects induced by the rf field:
1. RF-SIDEBANDS EFFECT
2. RF-COLLAPSE EFFECT
Rf-Mössbauer technique
1. RF-SIDEBANDS EFFECT
- frequency modulation of Mössbauer -radiation due to rfinduced vibrations of Mössbauer atoms via magneto-acoustic
coupling - magnetostriction
Sidebands positions - given by nr
intensities - frequency modulation (FM) model
Rf-sidebands can be observed in ferromagnetic
magnetostrictive materials (below the Curie point)
2. RF-COLLAPSE EFFECT
- magnetic radio-frequency field Hrf larger than the anisotropy field
HA (Hrf > HA)
- rf frequency rf larger than Larmor frequency L (rf > L)

fast reversal of magnetization

fast relaxation of the hyperfine field

hyperfine field is averaged to zero
Magnetic hyperfine structure in Mössbauer spectrum disappears
 the rf-collapsed spectrum: only QS doublet or a single line (the
sample is in the ferromagnetic state).
RF-collapse - very sensitive to the relation between Hrf and HA
- thus HA can be scanned by changing Hrf
RF-collapse can be observed in soft ferromagnetic materials
Rf-collapse allows the separation of magnetic dipole and electric
quadrupole hyperfine interactions in the ferromagnetic state
Rf-Mössbauer Results
1. Co-free alloy
no rf field
rf field: 20 Oe
1.00
1.00
a
a'
0.98
as-q
0.96
1.00
1.00
b'
b
0.99
0.98
Relative transmission
470oC
0.96
1.00
1.00
c'
c
0.96
0.99
o
520 C
1.00
1.00
d'
d
0.98
0.99
570oC
1.00
1.00
e'
e
0.99
0.96
670oC
-8
-4
0
4
8-8
-4
Velocity [mm/s]
0
4
8
Conventional Mössbauer spectra :
- as-quenched alloy- fully amorphous
- nanocrystallization: at 470 – 670oC
The dominating phase - bcc-FeNi accompanied by
the (FeNi)23B6 phase.
Rf-Mössbauer spectra
- the as-quenched alloy and annealed at Ta= 470oC
- rf-spectra - a collapsed doublet accompanied by rf
sidebands.
The alloy is magnetically very soft and
magnetostrictive.
- at Ta  520oC the collapsed pattern - single line - very
soft bcc-FeNi phase; the rf sidebands vanished.
- at Ta  570oC - rf-collapse incomplete.
The Mössbauer spectra recorded before and after rf
exposure are identical.
2. Co-containing alloys
Co10 alloy:
As-quenched alloy:
Addition of Co to the amorphous structure increases the anisotropy field.
-The full collapse of mhfs occurs at higher intensity of the rf field (16 Oe).
-The rf-sidebands of high intensity are observed.
-A larger Co-content causes the instability of the amorphous phase during
exposure to the rf field as a result of which the amorphous alloy crystallizes partly
due to the rf field exposure.
Co-containing nanocrystalline alloys:
The anisotropy field strongly increased.
-The rf-spectra of Co10 alloy (Ta470-570oC, rf field 20 Oe at 61 MHz) a central doublet accompanied by partially narrowed mhfs.
- No rf-sidebands.
- At Ta=620oC: rf-spectra do not depend on the rf field intensity and show mhfs of
FeCo phase (no rf-collapse, no rf-sidebands).
Co20 alloy:
As-quenched alloy:
520oC
as-q
620oC
1.00
1.00
a
a'
0.98
a''
0.96
0 Oe
1.00
1.00
b'
b''
Relative transmission
b
0.98
8 Oe
0.99
0.96
1.00
1.00
c'
c''
c
12 Oe
0.96
0.99
1.00
1.00
d'
d
d''
0.98
0.99
20 Oe
1.00
1.00
e'
e
0.98
e''
0.96
0 Oe
after rf
-8
-4
0
4
8 -8
-4
0
4
8-8
-4
0
4
8
- rf collapsed pattern
+intense rf sidebands
Annealed alloy:
- at Ta  520oC:
noncollapsed mhfs (FeCo
phase) (large anisotropy
limits the rf collapse) +
collapsed doublet
(amorphous matrix)
- at Ta = 620oC:
rf-spectra do not depend
on the rf field - mhfs of
FeCo phase
large anisotropy field
Velocity [mm/s]
The magnetostriction of the nanocrystalline alloy vanished;
the rf sidebands are not observed.
The Mössbauer spectra recorded (without rf field) for the alloys
(Co-free and Co-containing) before and after the rf field
exposure:
- are identical in the case of Co-free alloys, i.e., no rf
induced crystallization;
- are significantly different in the case of Co-containing
alloys - rf- induced crystallization.
The rf induced crystallization is attributed to mechanical
deformations induced in the sample via magnetostriction
(rf-sidebands effect).
Measurements of the quasi-static hysteresis loops [6]
B[T]
- the magnetic induction B (magnetization) and coercive fields HC
were estimated.
The coercivity in the Cocontaining alloys strongly
c
b
a
increased after annealing:
d
a: 470C
b: 520C
c: 570C
d: 620C
e: 670C
0.5
e
Co20-alloy:
H[A/m]
0.0
-20000
-10000
0
10000
20000
-0.5
The hysteresis loops recorded for
Fe41Ni20Co20Zr7B12 alloy
The smallest coercivity, 15 A/m was
observed at Ta=520oC, then increased to
783 A/m (Ta=570oC) and 4726 A/m
(Ta=620oC). The largest value (13113 A/m)
was reached at Ta=670oC.
The changes in coercivity reflect the
FeCo phase abundance in the alloys.
The measurements of the hysteresis loops fully support the rf-Mössbauer results.
Conclusions
The rf-Mössbauer results show that:
• The amorphous precursors are magnetically very soft.
• The anisotropy field increases with the introduction of Co
- in the amorphous alloy - this effect is significant
- in nanocrystalline alloys - this increase is dramatic.
• The rf-Mössbauer measurements are very useful for the estimation
of magnetic anisotropy fields.
• The presence and the magnitude of the rf sidebands provide direct
information regarding the magnetostriction of the alloys.
• The rf sidebands vanish when the magnetostriction becomes
negligible due to formation of the nanocrystalline structure.
• A novel effect - the rf-induced crystallization, of nonthermal origin,
of Co-containing alloys attributed to magnetostriction.
The rf field applied was able to induce the fast magnetization
reversal (rf-collapse) only if the rf field intensity was markedly
larger than the anisotropy field.
The rf-collapse effect was suppressed when the anisotropy field
became comparable to or larger than the rf field intensity.
In the Co-containing alloys both coercive fields and anisotropy
fields strongly increase at higher annealing temperatures.
References:
1. A. Makino, T. Hanai, A. Inoue, T. Masumoto, Mater. Sci. Eng. A 179/180,
552 (1994).
2. M. Kopcewicz, B. Idzikowski, J. Kalinowska, J. Appl. Phys. 94, 638 (2003).
3. M. Kopcewicz, Strutural Chem. 2, 313 (1991).
4. M. Kopcewicz, in G.J. Long, F. Grandjean (Eds) "Mössbauer Spectroscopy
Applied to Inorganic Chemistry" vol. 3, Plenum, N. York, London, 1989, p.
243.
5. M. Kopcewicz, J. Alloys and Comp. 382, 165 (2004).
6. T. Kulik, H.T. Savage, A. Hernando, J. Appl. Phys. 73, 6855 (1993).
These results were presented at the Magnetism and Magnetic
Materials Conference (MMM-2005), San Jose, CA, (USA) in
November 2005 and were published in the Journal of Applied
Physics 99, 08F112 (2006).