CHINESE JOURNAL OF PHYSICS VOL. 16, NO.

4 WINTER 1978

Magnetic Phase Transition in Nickel-Rich Nickel-Copper Alloys*

Y EONG D ER Y AO (&D,jc&) and J. H. EM (M%i:)

Institute of Physics
Academia Sinica
Nankang, Taipei, Taiwan

(Received September 8, 1978)

The electrical resistivity, p,. of a set of nickel-copper alloys has been studied
between 300K and 700K. Our data show that each of the ,o vs. T curves exhibits
a well-defined knee in the critical region of the magnetic phase transition; besides,
the temperature dependent part of the electrical resistivity follows a T.7*J.09
variation in the ferromagnetic region and increases more slowly than T in the
paramagnetic region. The concentration dependence of the Curie temperatures
of these Ni-Cu alloys has been determined from (dp/dT) vs. T analysis. It is
demonstrated that the dp/dT method and the kink-point method1 give identical
results.

INTRODUCTION

lR BCENTLY there are extensive studies on the effects of structural, electronic, compositional and
magnetic order-disorder of various metal and alloy systems. The magnetic properties of matter
were apparently discovered several thousand years ago, i. e., several thousand years ago, in China, the
natural permanent magnet was used practical purposes; we believe this is the most ancient account
of magnetism. However, a science of magnetic properties of matters actually began to develop
during the 19th Century. Till last year (1977), the Nobel Prize of Physics was awarded to three
physicists (John H. Van Vleck, Philip W. Anderson and Nevill Mott) for their fundamental theoretical
contributions of the electronic structure of magnetic and disordered systems. A number of fundamental
theoretical aspects of the magnetic properties of matter are still under investigating now, so we can
say that the science of magnetic properties of matter still abounds with mysteries.
It is well known that the characteristic feature of a metallic system is the presence of conduction
electrons. Electrical resistivity (or conductivity) is one of the most important properties, essentially
depending on the electronic, structural, compositional and magnetic situations of the metallic system.
In other words, the electrical resistivity of a given metal or alloy depends not only on its electronic
structure, but also on the mechanisms of the relaxation of the conduction electrons which are due
to the scattering by structural defects of the lattice, phonons, magnons and also due to the scattering
arising from electron-electron interactions. ,The electrical resistivity of simple non-transition metals
is mainly determined by the first two mechanisms of scattering. For non-magnetic transition metals,
especially at low temperatures, the last mechanism is essential. For magnetic transition metals, all
the above-mentioned mechanisms of scattering make contributions to the electrical resistivity.
For magnetic alloys, it has been amply demonstrated that electrical conduction at low tempera-
tures takes place by two currents in parallel, corresponding to majority and minority spin carriers,
respectively.2-5) As was suggested by Mott (5~) scattering events with conservation of spin direction
* Work supported by the National Science Council, Republic of China.
( 1) P. J. Wojtowicz and M. Rayle, Phys. Rev. Lett. 20, 1489 (1968).
( 2) I. A, Campbell, A. Fert and A. R. Pomeroy, Phil. Mag. 15. 977 (1967).
(3) A. Fert, J. Phys. C.: Solid St. Phys. 2, 1784 (1969).
(4) A. Fert and I.A. Campbell, J. Phys. F: Metal Phys. 6, 849 (1976).
(5) J. W. F. Dorleijn, Philips Res. Repts. 31, 287 (1976).
(6) N.F. Mott, Proc. Royal Sot. A1.53, 699; A156, 368 (1936).
(7) N. F. Mott, Adv. Phys. 13, 325 (1964).

189

l&d--.... .. .
190 MAGNETIC PHASE TRANSITION IN NICKEL-RICH NICKEL-COPPER ALLOYS

become much more probable at temperatures below Curie temperature than scattering events in which
the spin direction is changed. It is clear that the Fermi surfaces for majority and minority electrons
can be very different and their is no reason to assume equal relaxation times or conductivities for the
two spin currents. For the simplest two current model with two equal groups of free electrons,
each having the same effective mass, it was showed (2-4J that the resistivity can be described by

where P, and pi are the sums of the impurity resistivity and the temperature-related resistivity in the
spin-up and spin-down bands. The spin-mixing resistivity is characterized by 0,. When ptl=O, we
have a rigorous two current model.
In recent years, the study of the electronic resistivity anomaly in the vicinity of ferromagnetic
phase transition has received a good deal of attention.(814) According to Fisher and Langer@),
Richard and Geldart), the magnetic component of dp/dT above T, should vary like the magnetic
specific heat, i.e. it is proportional to E-=, where E= 1 T-T, 1 /T, and a is the specific heat critical
exponent. Below T,, dp/dT should be proportional to E~B-I, where p is the critical index for the
spontaneous magnetization. The divergence is positive both above and below T, . The Curie tem-
perature occurs at which d,a/dT diverges and there is no cusp in the p vs. T curve. However,
recently Su et a1,(12-) basing on the itinerant model and band calculation of pure nickel, show that
dp/dT is divergent linearly and positively below T,. It is, definitely, of interest to do further inves-
tigation about the electrical resistivity anomaly near the Curie temperature.
The electrical resistivity of ferromagnetic alloys exhibits unusually strong temperature dependences
in the temperature range in which the magnetic order changes significantly. One of the best under-
stood system is the nickel-rich nickel-copper system; copper is diamagnetic noble-metal and nickel is
ferromagnetic transition-metal. When copper is added to nickel the resulting alloy is less ferro-
magnetic. Following the simple band model concept, the addition of Cu to Ni should increase the
number of electrons in 3d band until this band is filled, and therefore, should increase the number
of electrons in 4s band. According to Mathon (15), the spontaneous magnetization, M, can be shown
as
M2= (a/2b)(X, - X), (2)
where a: and b are arbitrary constants and X, is the critical concentration for the onset of ferro-
magnetism. For Ni-Cu system, X, was suggested to be 0.56 by Hicks er aZ.06) and 0.53 by Panissod).
In general, the onset of ferromagnetism is necessarily preceded by a mictomagnetic region. In this
paper, we present a study of the electrical resistivity of nickel-rich nickel-copper alloys as a function
of temperature between 300K and 700K, and try to get further understanding about ferromagnetic
alloy system. It is demonstrated that the dp/dT method and the kink-point method) give identical
results.

EXPERIMENTAL CONSIDERATION
Five nickel-copper alloys, containing 0.0, 4.6, 9.3, 14.0 and 18.8 at.% copper were prepared by a
laboratory arc melter. It is a water-cooled type melter. A commercial rectified d. c. welding unit
(8) P. G. deGennes.and I. Friedel, J. Phys. Chem. Solids 4, 71 (1958).
(9) M. E. Fisher and J. S. Langer, Phys. Rev. Lett. 20, 665 (1968).
(10) T. G. Richard and D. J. W. Geldart, Phys. Rev. Lett. 30, 290 (1973).
(11) D. J. W. Geldart, T. G. Richard, Phys. Rev. B12, 5175 (1975).
(12) D.R. Su and T.M. Wu, J. Low Temp. Phys. 19, 481 (1975).
(13) D.R. Su, J. Low Temp. Phys. 24, 701 (1976).
(14) C.D. Hu and D.R. Su, J. Low Temp. Phys. 31, 527 (1978).
(15) J. Mathon, Proc. R. Sot. A306, 355 (1968).
(16) T. J. Hicks, B.D. Rainford, J. S. Kouvel, G.G. Low and J. B. Comly, Phys.Rev. Lett. 22, 531 (1969).
(17) P. Panissod, J. Physique 35, C4-173 (1974).
 YEONG DER YAO AND J.H. TSAI 191

is used as the electrical power supply. After repeated melting, the ingots, weighing about 10 grams
were sealed into silica tubes under l/5 atm. pressure of argon gas at room temperature and
homogenized at about 1200K for six days. From these alloys, samples in the form of rectangular
parallelepipes were cut. The surfaces of these samples were polished by using files and emery-papers.
Typical sample dimensions were roughly 1.5x 1.5x7 (units in mmJ). Four copper electrodes were
lightly spot-welded to each sample. The center two copper electrodes were used as the potential
leads; the other two were used as the current leads. The width, thickness and distance between the
two potential leads were determined by means of a very accurate vernier caliper.
Because not all samples were perfectly regular bars, the accuracy varied from one sample to
another. However, any resulting error in the form factor from these room temperature measurements
is not greater than 1%. Here, the form factor is defined by the crossection area of one sample
divided by the distance between the two potential leads. The electrical resistivity of the above
samples was determined using the conventional four-probe technique. Temperatures between 300K
and 700K were achieved in a Marshall vacuum furnace. Two chromal-alumel thermocouples were
placed near the two ends of the sample. A precision current source, with part in lo5 accuracy, was
useA as a constant current source. The voltages between the potential leads were determined with a
precision potentiometer (No. 7600, W. G. Pye & Co. Ltd.) with the necessary preamplifier_and galva-
nometer. This system was capable of detecting changes of 100 volt.

RESULTS AND DISCUSSION

The concentration dependence of the electrical resistivity at 273K of our Ni-Cu samples as well
as that due to Sevensson(18) is presented in Fig. 1. It shows that our samples are in good agreement
with that prepared by Sevensson. This confirms the expected good quality of the samples prepared
for this study. Fig. 1 also exhibits that the electrical resistivity has a maximum value near the fifty
per cent concentration. Fig. 2 shows the electrical resistivity of our Ni-Cu alloys containing 0.0,
4.6, 9.3, 14.0 and 18.8 at.% Cu between 300K and 700K. The p vs. T curves undergo an abrupt
slope change which results from a ferromagnetic-paramagnetic phase transition. It is obvious that
the Ni-Cu system is a typical normal nickel alloy system as shown in the Ni-Ti system.(lg)
It appears to be a standard practice to talk about a typical metal or alloy whose electrical
resistivity, p(T), as a function of the absolute temperature T, can be written as

where p0 is the residual electrical resistivity independent of T, and pi(T) is the temperature-dependent
electrical resistivity. The quantity p,, is due to the scattering of electrons from chemical and struc-
tural imperfections. The term pi(T) is assumed to result from the interaction of electrons with
phonons, magnons etc. Usually, pi(T) is expressed by a simple power law of T in a special tempera-
ture region; i. e. Pi(T)m T" , where n is any positive or negative numbers.
Our data were fitted to the empirical formula:
P(T)=PL~+AT" , (4)
where pleZ is estimated from both reference 20 and the extrapolation of our liquid-nitrogen-tempera-
ture resistivity measurements to 4.2K. The relative error from this procedure is less than 10%. A
plot of en (~-p~.~) against en T is shown in Fig. 3, which includes all the samples that we have
measured. From this plot, the index II comes out to be 1.74*0.05 in the ferromagnetic region.
And, in the paramagnetic region, the index n seems gradually changed from 0.9 for pure nickel to
0.6 for Mi-Cu sample containing 18.8 at.% Cu. It is evident that the temperature-dependent part of
the electrical resistivity increases faster than T in, the ferromagnetic region, this is due to the spin
ordering effect and the complicated combination of the interactions between electrons, phonons, and
__~ ___~ -.
(18) B. Svensson, Ann. Phys. 25, 263 (1936).
(19) Y.D. Yao, S. Arajs and K. V. Rao, Chin. J. Phys. 15, 1 (1977).
(20) J. C. Ododo and B. R. Coles, J. Phys. F: Metal Phys. 7, 2393 (1977).
192 MAGNETIC PHASE TRANSITION IN NICKEL-RICH NICKEL-COPPER ALLOYS

1
T=273 K ~
I

0 This Study

A Svensson

0 50

x (Io-*l

Fig. 1. Electrical resistivity of Ni-Cu alloys as a function of copper concentration at 273K.

e . . * b
. .
. ,
aG
+
. .
.
. .

- 0,o
.
zo- - .

.
. * +
.

1 .
.
.

10

300
1. . :

LOO 503 600

_J
700

TLKI
Fig. 2. Electrical resistivity of Ni-Cu alloys as a function of absolute temperature
between 300K and 700K.
 YEONG DER YAO AND J. H. TSAI 193

N I,_,CU, ..
3

s 3
1
e
r
=T

. l
.

.
.
.
2 I

, 6.0 6.5

.!n T
Fig. 3. (p-~,.~) against T on a en-en plot.

magnons. Generally speaking, there is always a Te contribution to the total electrical resistivity due
to ferromagnetism(zl~ez); and the contribution to the total electrical resistivity due to phonon at high
temperature is roughly proportional to T. Therefore, the combination of those interactions contributes
to the total electrical resistivity a T* term, where n has the value between 1 and 2. In paramagnetic
region, the temperature-dependent part of the electrical resistivity increases more slowly than T; this
can be explained in terms of straightforward band concept. According to Mott(J>7) and JoneP), the
convex curvature of pi(T) in the paramagnetic region can be given approximately by QimT(l-BT).
The coefficient B can be represented by:
dN,(E)
-& -if@- E=EF
(5)
where E is the energy, Nd(E) is the electronic density of states of d electrons, K is the Boltzmanns
constant and EF is the Fermi energy. The departure of the resistivity from linearity with temperature
is determined by the magnitudes and signs of Nd and (d NJEg etc. For nickel and nickel-rich alloys,
(d N&E)+ is big owing to the location of the Fermi energy near the maximum of the d-band.
Starting from pure nickel, if we increase the concentration of the copper impurity, the values of Nd
and (d NpIdE),, are gradually changed. This phenomenon has been demonstrated by the X-ray
photoemission spectra for Ni-Cu alloys reported by Htifner et a1.@4). We believe this is the main
reason why *the value of the index n is gradually changed from 0.9 for pure nickel to 0.6 for the
Ni-Cu alloy containing 18.8 at.% Cu.
Fig. 4 presents (dp/dT) vs. T curves of these Ni-Cu alloys in the temperature range between
300K and 700K. The solid curves in Fig. 4 were plotted as the best fitting curves from our data
(21) G. K. White and R. J. Tainsh, Phys. Rev. lett. 19, 165 (1967).
(22) F. C. Schwerer and J. Silcox, Phys. Rev. Lett. 20, 101 (1968).
(23) H. Jones, Handbuch der Physik 19, 227 (1956).
(24) S. Hiifner, G. K. Wertheim, R. L. Cohen and J. H. Wernick, Phys. Rev. Lett. 28, 488 (1972).
 MAGNETIC PHASE TRANSITION IN NICKEL-RICH NICKEL-COPPEK ALLOYS

0.3
Ni,_,Cu,

x -.ooo

x-386 x-v+0 x- ,093 x-~OLS

3 LUU XJU DUU IO

T l"K1
Fig. 4. Temperature derivative of the electrical resistivity of Ni-Cu alloys as a
function of temperature between 300K and 700K.

Ni,_,Cu X

q
LOO \
>\ X E. E. Anderson et. al
\
-k \ 0 This Study
300 \
\ .
(K I \ T. J. Hick &al.
\ b
\ D. A.Gugrra et. al.
2 \
\
\
\
\
0 \
100 - \

i-YA. >
00 I
10
I

20 30
I 1

LO
I

50
t t

60
I

70

x m-*1
Fig, 5. Ferromagnetic Curie temperatures of Ni-Cu alloys as a function of Cu
concentration.

i_-.-_,
 YEONG DER YAO AND J.H. TSAI 195

points using the least square method. The Curie temperature T, is determined from this plot as
the temperature at which dp/dT diverges. The values of T, determined from this analysis are shown
in Table I and Fig. 5. According to the previous low field magnetization study of the nickel-copper
alloys(Z5), the Curie temperatures were determined using the kink-point method) . The samples
used in this magnetization study were made spherically with diameter about 3 mm. Both determina-
tions, i.e., &/dT and kink-point technique, give identical results as shown in Fig. 5. From these
studies it is evident that T, decreases linearly with a slops of 11K per at.% of Cu. The extrapola-
tion of this curve intersects the concentration axis at about 56% of Cu. This means that, near this
concentration, there is no hole in the d band, such that the ferromagnetism disappears. Recently,
Ododo and Coles(*Q reported that the critical concentration for the onset of ferromagnetism ,in the
Ni-Cu system is 52.4 at.% of Cu and that in general the onset of ferromagnetism in all giant moment
alloys is necessarily preceded by a mictomagnetic region. Fig. 5 also shows the experimental results
due to Hicks et al.() and Guerra et al.(ze). The agreements are quite reasonable.
Recently, Yao and Arajs(Z reported that Curie temperature of a set of ferromagnetic binary
alloys with different concentrations can be determined by means of the difference between the resisti-
vities of two samples at the same temperature. Further work on these analyses basing on the devia-
tion from Matthiessens Rule etc. of this Ni-Cu system is in progress and will be reported elsewhile.
Table I. T, of Ni-Cu Alloys

Tc (K)
Cu concentration (at.%) .__~~~ _ _ _ _ _
This study Ref. 25
_--
0.0 627+1 626.055&0.005
4.6 576&l 575.60 zkO.01
. 9.3 526+1 525.95 -+O.Ol
14.0 475*1 475.39 *0.04
18.8 425+1 424.9 -10.3

_.--_._____ __.- _.~..~ ~_. .-.-

(25) E. E. Anderson, S. Arajs, A. A. Stelmach, B. L. Tehan and Y. D. Yao, Phys. Lett. 36A, 173 (1971).
(26) D.A. Guerra and P. Panissod, J. Phys. F: Metal Phys. 7, 521 (1977).
(27) Y.D. Yao and S. Arajs. Bull, Phys. Stat, Sol, (b)89, K201 (1978).

-- ^