361

The Electrical and Magnetic Properties of the Uranium-Niobium

System

BY L. F. BATES AND R. D. BARNARDt

Department of Physics, University of Nottingham

MS. received 3rd March 1961

-4bstract. The magnetic susceptibilities and electrical resistivities of a series of

.,-phase uranium-niobium alloys were measured over the temperature ranges
$1200"~ and 90-1200"~, respectively. T h e form of the resistivity-
temperature-concentration relations is abnormal, especially at low temperatures,
where negative temperature coefficients of resistivity occur in the uranium-rich
alloys, and no explanation can be found in terms of localized moments on either
or Nb atoms. Comparison is made of the same properties of the y U-MO
doys and particular attention is directed towards the electronic band structure of
mobium. A rigid band model is shown to be appropriate for dilute solid solutions
of uranium and molybdenum, but such a model is not applicable to the uranium-
nch y U-MOand the U-Nb alloys.

Q 1. INTRODUCTION
E s E A R c H on the physical properties of the U-MO and U-Nb alloys has

R received impetus in recent years, following the discovery by Bleiberg,

Jones and Lustman (1956) that some of the metastable y body-centred
cubic alloys possess small negative temperature coefficients of resistivity below
room temperature. More recently, Chandrasekhar and Hulm (1958) studied the
electrical resistivity and superconductivity of a series of cc (orthorhombic) and
7 (body-centred cubic) binary alloys of uramum with molybdenum and niobium
between 1O and 295 OK. All the quenched y alloys in the range 15-30 at. yowere
found to exhibit anomalous negative temperature coefficients of resistivity.
lhgnetic susceptibility and electrical resistivity measurements on the y U-MO
~ O Y were
S made (Bates and Barnard 1961) over an extended temperature range
in order to include the stable y region, and it was concluded that no explanation
of the results could be given in terms of localized electrons on either the molyb-
denum or uranium atoms.
Inspite of these and other investigations (Loasby 1958, Blatt 1961, Berlincourt
1959), the origin of the unusual behaviour has not been completely explained.
It was therefore thought that more light might be shed on the problem by studying
he electrical and magnetic properties of the U-Nb system, where the y phase
could be retained in metastable equilibrium over a much larger composition
range than in the U-MO system. I n addition, it was hoped that a comparison of
he properties of the U-MO and y U-Nb alloys would provide information on
he electronic structure of y uranium, particularly on the density of states-energy
bsmbubon.
t Now at Research Laboratories of Electrical and Alhed Industries Research Association,
Leatherhead, Surrey.
PROC. P H Y S . SOC. LXXVIII, 3 2A
362 L. F. Bates and R. D . Barnard

No previous extensive investigation into the physical properties of the U-&

alloys has been made, but the phase diagram of the system is well established
(Pfeil, Brown and Williamson 1958). There is complete solubility above 9 s O O c
of y uranium and niobium, although with intermediate compositions below 9 5 0 0 ~
the state exists in two body-centred forms, y1 and yz. T h e y phase of samples
of composition greater than 20 at. % N b can be retained at room temperature by
quenching.
0 2. EXPERIMENTAL PROCEDURE
T h e alloys were prepared at the Atomic Energy Research EstablishmenL
Harwell, in an argon arc furnace from 99.9 % pure uranium (see Bates and Barnard
1961), and spectroscopically standardized niobium, supplied by Johnson Matthey
and Co. Ltd. T h e ingots were wrapped in molybdenum foil, sealed in quam
capsules under a pressure of less than 10" mm Hg, and annealed for two week
at 1 0 0 0 " ~ . T h e ingots were afterwards machined to give cylinders 4cm long and
5 mm in diameter, which were resealed, heated in the capsules, and quenched in
water from 1 0 0 0 " ~with fracture of the quartz. Microscopic inspection of the
specimens kindly performed at the Atomic Energy Research Establishment,
Harwell, showed for compositions above 30 at. yoNb the existence of the y body-
centred cubic phase in metastable equilibrium ; but, like the alloys of sirmlar
composition in the U-MO system, between 20 and 30 at. Yo Nb there was estab-
lished a distorted y body-centred tetragonal phase whose axial ratio was so close
to unity that the tetragonality was not observable by x-ray techniques. In
addition, the investigation showed that the alloys were not completely homo-
geneous despite the long time of anneal, the inhomogeneity being more marked
in the 20-70at. yo Nb range of composition. No observations of the lattice
parameters were made, as these were being performed concurrently at Harwell b\
Pfeil, Brown and Williamson (1958). T h e parameters were found to obey
Vegard's law fairly accurately, the addition of niobium contracting the lattice of
y uranium.
The experimental arrangements for the measurement of magnetic suscepb-
bility between 293 and 1200°K and for electrical resistivity between 90 and 12oo'h
together with a discussion of the experimental limitations have been described
elsewhere (Bates and Barnard 1961).
Alloys in the composition range 20-80at. yo Nb were first measured in the
metastable y state with rise in temperature until the y phase began to decompose
This was manifested by marked discontinuities in the slopes of the susceptibllln-
temperature and of the resistivity-temperature curves, at which juncture measure-
ments were discontinued until further rise in temperature took the specimens into
the stable y region. Having once in these alloys established the y phase, whlCh
is stable only at very high temperatures, it was possible to make measuremen!
with decrease in temperature into the y1 + y z phase region ; for precipitabon Ot
+
y to y1 y2 is so slow that the y phase does not decompose at temperatures neU
700°C, even after several days. Above 8OO"c, Pfeil, Brown and Williamson
(1958) reported that the transition from single phase y to y1+y2 does not OCcu
even after anneals of eight weeks duration. Each of the curves for these alloy
thus had a temperature region where no observations of the y phase could
made, but it was possible to interpolate between the observations in the mew
stable and stable y regions and so estimate with reasonable accuracy the form Of
 Properties of Uranium-Niobium Alloys 363

the curves where the Y phase was decomposing. For compositions above
80 at. yo Wb, the alloys were stable in the body-centred cubic modification for all
temperatures up to their melting points.
5 3.
EXPERIMENT.~LRESULTS
3.1. Mapzetic Susceptibility
The molar susceptibilities against temperature of the U-Nb alloys in both
metastable and stable y states are shown in Figs 1 and 2. In view of the inhomo-
geneity of some of the specimens, two values of the room temperature suscepti-
bility were obtained for each specimen (one in the inverted position) and the

3
E U -4at.gb'Nb
5 400-
/n
_ _ _ - -- --__
- _--- --aA+----n
-
v

-0

2 380-
A
- - ---
_ _ _- _- _- _ - - -
_ _- - - * A
.e
5 3 6 0 -- - -
a
U
_ _ - -- --- -
_ _ - - _- _ - - -/- --
Ma-

3*0; I I I I J I
200 400 WO BGO 1000 12w
OK

Fig. 1. Susceptibility plotted against temperature for y U-Nb alloys.

Fig. 2. Susceptibility plotted against temperature for y U-Nb alloys.

mean taken as the correct value. With no specimen was a difference of more than
2% found between measurements when the specimen was inverted, to bring
another portion of the specimen into the region of maximum field gradient.
It is clear that the addition of niobium to y uranium gives a general reduction,
not only of the magnitude of the susceptibility, but also of the temperature
coefficient. The temperature coefficient of susceptibility of U-25 at. % Nb is
positive, as in the U-MO system, and gradually decreases with increasing niobium
ZA2
364 L. F. Rates and R. D . Barnard

concentration until it is negative as with pure niobium. T h e results for

niobium are in close agreement with those previously recorded (Kriess" 19531,
the variation with temperature being fairly linear over the range of temperame
investigated. The absolute value at room temperature was 2-29 f 0.02 x 104
e.m.u. g-1, a value rather higher than that recorded by Kriessman, but 111 close
agreement with that recorded by Williams (1960 unpublished), viz. 2.3 x 104
e.m.u. g-l.
TWO of the niobium-rich alloys, U-70,80 at. % Nb, exhibited shallow susceph.
bility minima at about 5 0 0 " ~and 9 0 0 " ~ ,respectively. This tendency for a
minimum to exist and for it to shift towards higher temperatures with incralng
concentration of niobium is most unusual, but it is interesting that Kriessm
observed a minimum in observations on pure niobium at about 2000"~.
T h e isothermal susceptibilities at O"K and 1100°K are shown as functions of
composition in Fig. 3. The O'K values were obtained by extrapolation from &e

EL-Ll?s
Susuptrbilitits a t llW°K
x Extrapolated wxeptrbilities to O k
v)

180 IO 20 30 40 A t50%Nb 60 70 80 90 loo

Fig. 3. Susceptibility plotted against composition for y U-Nb alloys.

observations above room temperature shown in Figs 1 and 2. They are pm

cularly interesting; firstly, because small additions of uranium to niobium dd
not alter the susceptibility, and secondly, because the susceptibility curve !\hen
extrapolated to zero niobium content yields a value in close agreement with
obtained from work on the U-MO alloys (Bates and Barnard 1961). Tht
constancy of the susceptibility of the niobium-rich alloys is very remarkable-
especially in view of the different, conventional valencies of uranium and
niobium. This point is considered in greater detail in the discussion belo!\.

3.2. Electrical Resistivity

The resistivity-temperature curves for uranium-rich alloys, shown In Fig. i,
are characterized by behaviour very similar to that of uranium-rich U-MO
i.e. by a negative temperature coefficient of resistivity for the quenched do!s
Increasing concentrations of niobium reduced the magnitude of the negau\(
temperature coefficient and the magnitude of the positive coefficient in the stabit
y region. This abnormal behaviour persisted to 60 at. yo Nb, Fig. 5, and ben
more or less normal behaviour prevailed, Fig. 6, to pure niobium.
 Properties of Uranium-Niobium Alloys 365

._-----
__ _--- - /*
/=
_----
_-+---

I U-30atJNb
II U - N a t X N b
/=
I m U - IOatXNb
I U - Pure Uranium
/=

Fig. 4. Resistivity plotted against temperature for y U-Nb alloys.

-2
I I U-80at.%Nb
n U-%at%Nb
Ill U-pure Niobium

Fig. 6. Resistivity plotted against temperature for y U-Nb alloys.

3 66 L. F. Bates and R. D. Barnard
The resistivity curves of pure niobium and the niobium-rich alloys
like those of many other transition elements, temperature Coefficients
decrease with temperature. This effect is considered below in greater dew 1o
the discussion of the density of electron states against energy curve for pure
niobium.

2o

0
t
1
x Extrapolated resistivitres to 0%

1
IO
I
20
I
30
I
40
At
4
50
7 Nb
I
60
I
70
1
EO
I
W IW

Fig. 7. Resistivity plotted against composition for y U-Nb alloys

The resistivity with composition curves, shown in Fig. 7, exhibit denatlous

from normal alloy behaviour. The curve for the resistivities at O'K, obtainedbi
extrapolation of the resistivity-temperature curves indicates an extremely hl@
value for the resistivity of pure y uranium when the curve is extended. Ths U
of course, unacceptable ; in addition, the variation with composition at 1 1 0 0 ~ ~
concave upwards at the uranium-rich end, in contrast with the concave dom
wards curve given by the equation
poOcx(1 - x ) . . . ... . ( I )
Here po is the residual resistivity and x the concentration of one element in thc
other. Eqn (1) gives a maximum in the residual resistivity curve at 50 at. $ ' ,%
the maximum observed here is at about 64 at. yo Nb.
No previous work on the magnetic susceptibilities of these alloys has been
recorded, and only the low temperature resistivities of the uranium-rich do!S
have received attention, through the work of Chandrasekhar and Hulm (19V
Their numerical results are in excellent agreement with those presented abov

0 4. DISCUSSION
Striking similarities exist between the present results for the U-rich
alloys and those for U-MO alloys (Bates and Barnard 1961). These
essentially (1) strong positive temperature dependence of susceptibilities in
case of the metastable alloys and almost no temperature dependence in the
y regions; ( 2 ) negative temperature coefficients of resistivity in the case oft
metastable y alloys, and weak positive dependence in the stable y regions; (J'
similar resistivity-concentration and susceptibility-concentration curves.
 Properties of Uranium-Niobium Alloys 3 67

The similarities in the results would seem to indicate that an explanation like
hatfor the y U-MO alloys is appropriate, although there is no indication as to
,&y Nb and MO behave in the same manner in y uranium. Briefly, then, the
,,ceptibility results for the U-rich U-Nb alloys are compatible with the Fermi
surface lying in each case in an energy region for which
A-B>O ...... (2)
shere

Here, N is the density of states per unit energy per mole, and E, is the Fermi
energy measured from the band edge. T h e density of states against energy
Cures for these alloys are thus concave upwards at the Fermi surface. T h e failure
,f the susceptibilities to give T 2variations, especially at high temperatures, may
be due to the failure of the degeneracy condition
E,$kT. ......(3)
The susceptibility results, Fig. 2, further indicate that at about 60at. % N b the
Inequality (2) becomes A - B = 0, to change to A - B < 0 at higher concentrations
of niobium.
A s in the discussion of the U-MO alloys one notes that a negative temperature
coefficient of resistivity may arise if
3B-A>O, ......(4)
and if the residual resistivity is large compared with the thermal resistivity given
by the Gruneisen expression. T h e latter condition is, of course, likely to be
satdied at fairly low temperatures where the unusual behaviour is in fact observed.
Further, the residual resistivities are large, Fig. 7, for the U-rich alloys, and the
weak concentration dependence is indicative of a large increase in the effective
number of free electrons with composition. It is thus evident from the present
Lscussion that the Fermi surfaces in both the U-rich U-MO and U-Nb alloys lie
111 regions where the density of states-energy curves possess finite gradients of
strong positive curvature.
Since in the uranium-rich U-Nb alloys the addition of N b with five valency
electrons depletes the band of the solvent, the application of a rigid band model
should lead to a curve of the variation of the density of states with solute concen-
tration which is concave upwards. The variation of susceptibility at O'K with
composition shown in Fig. 3 may be taken to represent the variation of the density
of states with niobium content provided that the empirical relation (Childs,
Gmher and Penfold 1960)

...... (5)
Evdld, where K is the exchange interaction and C is a constant. This variation
Isconcave downwards for the low niobium content alloys, and so it appears that
addtion of N b to U in concentrations greater than 20 at. yonot only alters the
degree of occupation of the bands but also their ( N ( E ) ,E ) relation. I t should be
Itmarked that values of K and N(E,) for both the U-MO and pure niobium
obey the relation (5) fairly accurately.
3 68 L. F. Bates and R. D. Barnard

I n a discussion of the magnetic properties of the transition elements,

Kriessman and Callen (1954) concluded that, if the Pauli susceptibility decreased
with temperature, the Fermi surface was near a maximum in the density of
curve. Such susceptibility behaviour is exhibited by pure niobium, a d thus
little change of susceptibility should result when m" which enhance the
degree of occupation of the bands of niobium, is added in small quantities. ~h
argument is clearly supported by the susceptibility-composition curves shown
Fig. 3, and also by similar results on the N b M o system (Matthias et al. 1960).
Additional evidence that this band shape is correct for pure niobium was obtained
by calculations of A and B from the susceptibility and resistivity data.
Values of A - B and 3B - A were obtained from the linear regions of plots
of the Pauli susceptibility against T 2and of p(E, T ) / Tagainst T 2 ,where p(E, T)
is the resistivity. That these plots should be straight lines is evident from the
formulae

xa; = 2$v(EO) [1 + Ty
( A- B ) ] E-%
.. . ...(6)
for the molar Pauli susceptibility xM' and

for the resistivity, where p(EoT)is the Gruneisen expression which is propomonal
to T in the temperature range under consideration. Above the Debye tem-
perature ( U 2 5 4 " ~ )and , plot of p ( & T ) / Tagainst T2was h e a r
, below 5 0 0 " ~the
The values of A and B thus obtained were

= -2.2 (ev)-*
and
B=
&:)-tI,(-- = 9.0(ev)-2.

The negative value for A clearly supports the previous discussion, as t iu

condition is essential for the Fermi surface to be near a maximum in the (N(E),E)
distribution. No great accuracy is claimed for these values of A and B, esped!
as the Pauli susceptibility was calculated on the assumption of a temperature
independent exchange interaction. It may well be that when consistent data 1s
available for the temperature dependence of the thermoelectric power and Hall
coefficient, the values will need modification.

ACKNOWLEDGMENTS
The authors are indebted to Dr. G. K. Williamson, formerly of the Metdurg!
Division, Atomic Energy Research Establishment, Harwell, and Dr. iV. E.
Gardner, for the provision of the alloys and also for much valuable discus~lo~
and to the Director, Atomic Energy Research Establishment, for permission to
publish the results.
 Properties of Uranium-Niobium Alloys 369
REFERENCES
L.F., and BAFWARD,R. D.,1961,Proc. Phys. Soc., 77, 691.
~ ~ ~ v T. R G.,T 1959,
, J. Phys. Chem. Solids, 11, 12.
”, F., 1961,J, Phys. C h . Solids, 17, 177.
”c, M.L.,JONES, L.I., and LUSTMAN, B., 1956,J. Appl. Phys., 27, 1270.
~ R A S B K H A R ,B. S.9 and HULM,J. K., 1958,J. Phys. Chem. Solids, 7, 259.
a m ,B., G ” E R , w. E., and PENFOLD, I., 1960, Phil. Mug., 5, 1267.
e.~, C., 1953,Rev. Mod. PIEys., 25, 122.
U”, C., and CALLEN,H., 1954,Phys. Rev., 94, 837.
b m y , R. G.,1958,P ~ o cPhys.
. SOC.,72, 429.
M.UTHIAS, B. T., PETER, M., WILLIAMS,H. I., CLOGSTON,A. M., CORENZWIT,E.,
SHERWOOD,R. c., 1960,Phys. Rev. Letters, 5, 542.
MIL.,P. C. L.,BROWN,J. D.,and WILLIAMSON, G.K.,1958,A.E.R.E. Report M/R 2498,