Solid State Communications, Vol. 13, pp. 1703—1706, 1973. Pergamon Press.

Printed in Great Britain

Ni K a1 AND Cu K a1 X-RAY EMISSION LINES FROM CuNi BINARY ALLOYS

M. Pessa and R. Uusitalo

Institute of Materials Research, University of Turku, SF-20500 Turku 50, Finland

(Received 29 August 1973 by 0. V. Lounasmaa)

The shape and energy of the Ni K a1 X-ray emission line is shown to depend
on the composition of CuNi alloys across the entire alloy diagram. The
magnetic transformation is clearly indicated in the width and position of
NiK a1 and the position ofCuKa1.

THERE is much experimental evidence that the dcc- This is because perturbations on the inner levels (ni)
tromc structure of the CuNi binary alloys is adequately of the iron transition elements are shown to be mainly
accounted for by the existence of spin degenerate produced by unpaired 3d electron 3 Anspins through
unbalanced
resonant bound
bound-state d-states
model”2 at the Fermi
together level. This
with another virtual-
approach 3d(nl) exchange integrals.”’
d-spin of nickel may therefore give rise, for example,
by Stocks eta!.3 based on the coherent-potential to perturbations on the 2p
4 and Veick~et al.,5 proposes 3/2 level of
there are at least two experiments, nickel.
known to In
thefact,
approximation
that the decreaseof in
Soven
the magnetic moment of the corn- authors, carried out on the K a 2P3’2) in
position with increasing Cu concentration cannot be an attempt to determine whether 1 line (Is alterations
possible
—

due to the filling of the Ni d-like band at the expense in the shape of K a
1 obtained from various CuNi alloys,
of the number of Cu 4s electrons
6 Considering as the rigid-band
experimental K, L and i.e.
large enough to be ferromagnetic
from para. and observable.14’15compositions, were
No definite con-
model assumes.
M X-ray emission band spectra from CuNi alloys7~° clusions, however, could be drawn from the results
one can indeed find a very limited alteration, if any, of those experiments.
among different compositions and this finding is fully
consistent with the virtual-bound-state model and the We have carefully re-examined the shape and
coherent-potential approximation. The magnetic trans- energy of Ni K a
1 and Cu K a1 for the range of con-
formation at 40—50 at.% Ni is not, however, indicated centration of the constituents across the entire alloy
in these bands, which merely show variation in the diagram. Copper—nickel ingots of composition 8,22.
relative intensities of the two characteristic band peaks 38, 53, 72 and 86 at.% Ni (in addition to pure nickel
according to the fractional abundance of the con- and copper) were prepared by melting in an induction
stituents. Nor is it possible to observe any sign of the furnace under argon gas and were then quenched in
different local magnetic environment of Ni and Cu liquid nitrogen. All the samples were severely cold-
atoms when placed in the para- and ferromagnetic rolled and then annealed at 800°Cfor 2 hr. These
alloys. One reason for this may be the fact that the homogenization procedures may have been too mild
d-bands of copper and nickel partly overlap each other to remove
16”8totally
On thetheother
clustering
hand weof Ni atomsthat
believe in the
the
and are spread over a relatively large energy interval. alloys.
formation of magnetization clouds, which appear most
It is conceivable that the effects of magnetic probably at about 50 at.% Ni, has only had a slight
surroundings on Cu and Ni atoms might be more influence on the final results, since our sample con-
perceptible if the sharp and intensive X-ray emission taming 53 at.% Ni did not indicate any anomalous
lines from some inner atomic core levels were studied, behaviour with regard to the gross parameters of the
spectral lines studied (cf. reference 19).
1703
 1704 Ni K a1 AND Cu K a1 X-RAY EMISSION LINES Vol. 13, No. 10

~ 2.6
•Cu K01
ON K~1 :~~
~
a6

-
\\ ~
REF. 21
~NCOND.~F
~ <~)REF22
21

~ -Dir-
J_____________
0 C~ ATOMIC ‘I.

iQ3C~ ATOMIC ‘/~

FIG 1. Line widths rand energy shifts ~E of Ni K a1

- FIG 2. Average 3d magnetic moment (?lNj> derived
-

(open circles) and Cu K a1 (darkened circles) measured from the change of r of Ni K a1 in the alloys (see text
from CuNi alloys. The straight lines are fitted to the and Fig. I). For comparison, (~>and PNi + Pcond
experimental points according to the least-square from reference 21 and (ii> from reference 22 are also
method. Error limits are shown by vertical bars. shown.

The present work has been made possible by a paramagnetic range, which effect may be an indication
new high-resolution X-ray fluorescence spectrometer of a slight permanent moment on Ni atoms in qualita-
which can attain a resolving power of 40,000 when the tive agreement with observations22 bysee
magnetization
also reference
third order
series Bragg reflection of two CaCO3 crystals in
is used.2° measurements
21. for Cu-rich
If we can really relate aalloys,
change in r to a change in
(bLN1) in the way described later, then a further con-
The half maximum width r of the Ni K a
1 and clusion is that the precision fluorescence method is
Cu K a1 lines, measured from the above alloys, and highly sensitive to the mean magnetic moment of
the line shift ~.E with respect to the corresponding individual atoms.
pure metals are shown in Fig. 1.
The variation of the spin moment of a Ni atom
The first interesting feature appearing in the due to the variation of the CuNi alloy composition
results is that the boundary of the paramagnetic and can be understood in terms of the local atomic environ.
ferromagnetic regions is clearly revealed both in r and ment without postulating any special clustering
2L23 of the
fl~
AEr of
in ofNiCuKKa1a and ~E of Cu K a1, but is not indicated constituents or the sharing of 3d electrons
1, at 50—60 at.% Ni, and this is in reason- picture is in close agreement with the experimental
able agreement with the expectations. These results observations of the mean magnetic
2’ Because ourmoment (~)of an
measurements are
suggestmoment
netic that theof increase of (PN1),
nickel (due theexistence
to the average 3d mag-
of the overall composition.
primarily concerned with the disturbance on the 2P3
12
unpaired 3d electrons), in the presence of chemical levels of individual Cu and Ni atoms in the field of
short-range order,~with the increase of Ni concen- (u), it is reasonable to assume that the change of <PNj>
tration is closely related to perturbations throughout
2P3/2 level. Secondly, is mainly
(the Zeemanresponsible
splittingfor
is antheorder
change of r of Ni K
of magnitude a1
smaller
theofwhole
r Ni K aNi atom down to the
1 shows a continuous increase even in the than the above interaction). In order to outline the
 Vol. 13, No. 10 Ni K a1 AND Cu K a1 X-RAY EMISSION LINES 1705
25’26 and is occupied by
approximate trend
on the basis of of (1.LNI) inofdifferent
the variation compositions,
r obtained we have lies 2electrons
the eV belowof the Fermispin.
balanced level The only contribution
chosen <#Nj> = 0.7 Bohr magneton for pure nickel24 to the magnetic moment is therefore a polarization of
and (~Ni>= 0 for a very dilute Ni alloy. The results conduction electrons. However, these electrons alone
thus obtained are shown in Fig. 2 together with (~) are not enough to explain the shifts measured for Cu
and PNi + l.z~Ud21 Here PNI is the 3d magnetic Ka
1 in the ferromagnetic alloys (Fig. 1). The copper
moment in the absence of any chemical short-range 4s and nickel 4s electrons are completely shared on
order and 1~nd the contribution of conduction dcc- account of the similarities of the 4s-bands of these
trons of nickel to the total magnetic moment of a Ni metals, this sharing 9resulting
if nickelinisaassumed
decreasetoofretain
the Cuits
atom
ment (for homogeneous
between our (1.tN1> alloys
and the(PNI> PNI). Agree-
= results
other is 4s electron density’
pure metal configuration 3d944s°6in the Ni-rich
moderate, in particular when the rough analysis of the alloys. On the basis of Clementi’s tables27 absence of
relationship between I’ and (PN~)made above is borne one Cu 4s electron from the free atom (with the Cu
in mind. For more accurate determination of the trend d-band occupied) would, however, cause a shift of
of the curves (not necessarily the straight lines we have + 0.12 eV in Cu K a
1, which is totally inconsistent
extrapolated) in Figs. 1 and 2, some additional alloys with our value —0.13 eV, extrapolated to 100 at.% Ni.
with different compositions would be needed. Hence the shift of Cu K a1 in the ferromagnetic region
21 that Cu atoms re- cannot be understood
4s electrons of copper by considering
atoms with thethe sharing of the
neighbouring
Recently
tam their smallit magnetic
has been moment
shown of the pure metal, nickel atoms. Instead, it seems possible that there is a
—0.1 Bohr magnetion, in the ferromagnetic alloys. To complete absence of coupling between the charge trans-
some extent this is corroborated by the results shown fer and the observed shifts of K a
1 of both copper and
in Fig. 1 where the r’-values of Cu K a1 follow a straight nickel in CuNi alloys. At the moment one can only
line with no discontinuity at the point of the magnetic conclude that ~E of Ni K a1 and Cu K a1 is clearly
transformation. The observed behaviour of r of Cu K related to the mean magnetic moment of the alloys.
aj is roughly what one might expect since the Cu d-band

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1706 NiKa1 AND CuKa1 X-RAY EMISSION LINES Vol. 13, No. 10

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II est démontré que Ia forrne et l’~nergiede Ia ligne d’émission des rayons

X Ni K a1 depend de Ia composition de l’alliage CuNi a travers le diagrarnme
d’alliages entier. La transformation magnCtique est indiquCe nettement par
Ia largeur et la position de Ni K Oi, et par la position de Cu K a1.