Polymorphic and peritectic phase transformations

of In3Zr studied using PAC

Lee Aspitarte
Washington State University
Department of Physics and Astronomy
February 2011

1 Introduction
It has been previously reported that In3 Zr forms the Al3 Ti (D022 ) and Al3 Zr
(D023 ) type structures, but the temperatures that these structures formed at
were not given.

Figure 1: The Al3 Ti(left) structure has two Al type sites. The Al3 Zr(right)
structure has 3 Al type sites.

The Al3 Ti structure has two inequivalent Al type sites designated Al(1) and
Al(2). Both of these sites have a high degree of axial symmetry. The Al3 Zr
structure is similar to that of Al3 Ti, and has the Al(1) and Al(2) sites as well.
There is one more site, designated Al(3). The Al(3) site lacks complete axial
symmetry.

1
2 Exerimental Methods
2.1 PAC
The phases of In3 Zr were analyzed through the method of perturbed angular
correlation of gamma rays(PAC). PAC is preformed by doping intermetallic
alloys, in this case In3 Zr, with radioactive 111 In probe atoms.111 In has a half
life of 2.8 days, where it then decays by electron capture into a long lived exited
state of 111 Cd. The 111 Cd decays from its exited state through a cascade of two
γ rays. The two ’start’ and ’stop’ γ rays signal the entry into and departure
from an intermediate state, respectively. This intermediate state has a mean
lifetime of 120 ns and a nuclear spin I=5/2. The main principle of PAC is
that the probability of the direction of emission of the second gamma ray can
be anisotropic with respect to the direction of emission of the first gamma ray
and the nuclear spin axis. Usually the radiation from a radioactive sample
is isotropic because the nuclear spins of the radioactive atoms are randomly
oriented. However, the direction of propagation of the first γ ray of the γ-γ
cascade, γ1 , will be perpendicular to the nuclear spin axis of the intermediate
state. The second γ ray will also be preferentially be emitted in the plane
perpendicular to the spin axis of the intermediate state. By detection of start
γ rays in by detectors in a certain plane, only nuclei with spin perpendicular to
this plane will be considered. This establishes an effective spin alignment.

2.1.1 Measurement of Hyperfine Interactions

For an angle Θ about the nuclear axis from the emission of γ1 the probability
to detect the second γ ray, γ2 , is given by:
X
W (Θ) = 1 + Akk Pk (Cos(Θ)) (1)
k

Where Pk (Cos(Θ)) are the Legendre polynomials and Akk determines the amount
of deviation from an isotropic correlation of the emissions of γ1 and γ2 . The
summation variable k depends on the angular momenta of the different states
involved in the decay.
In the presence of an electric field gradient, an atom with an electric quadrupole
moment will display a hyperfine splitting of energy levels. For a difference in
energy ∆E between two spin states, The atoms will undergo a Larmor preces-
sion. The anisotropy of direction of emission will precess with the atom, and
W (Θ) will be come time dependent through the time dependent perturbation
factor Gkk (t):
X
Wkk (Θ, t) = 1 + Akk Pk Gkk (t)(Cos(Θ)) (2)
k

and
i
Gkk (t) ∝ e h̄ (∆E)t (3)

2
 The intermediate state of Cd111 has a nuclear spin I=5/2, and three spin
projections |m| = 1/2, 3/2, 5/2 . In an electric field gradient there will be three
different energy energy levels. The difference in energy between the |m| = 1/2
and |m| = 3/2 states is not the same as the difference between the |m| = 3/2
and |m| = 5/2 states. Therefore the intermediate state of Cd111 undergoes
three spin precession frequencies. In the case of axial symmetry at the site of
the probe atom, These frequencies are in the proportions ω1 : ω2 : ω3 = 1 : 2 : 3
. For I=5/2, k=2, and The perturbation function G22 (t) takes the form:
1 13 10 5
G22 (t) = (1 + Cos(ω0 t) + Cos(2ω0 t) + Cos(3ω0 t) (4)
5 7 7 7

2.1.2 Axial symmetry

An Important characteristic of the lattice locations that the In probe atoms
occupy is the axial symmetry of EFGs at the site. The symmetry of the EFG
at a site is described by the asymmetry parameter η:

η = (Vxx − Vyy )/Vzz (5)

Where
∂2
Vxi xi = V.
∂x2i
V denotes the electric potential at the lattice site, and Vzz is by convention
the largest component of the EFG . Therefore the axially symmetric case will
be when Vxx = Vyy . Also, by the convention Vxx ≤ Vyy ≤ Vzz , η has the
range 0 ≤ η ≤ 1. η is measurable at a lattice location because the asymmetry
of EFGs will distort the hyperfine energy structure from that described in the
axially symmetric case earlier. The Hamiltonian of a nucleus with quadrupole
moment Q and spin I in an EFG of magnitude Vzz is generally given by:
eQVzz η 2
H= (3I 2 − I(I + 1) + (I+ 2
) + (I− ))
4I(2I − 1) z 2

In the case of non axial symmetry (η > 0) The angular momentum raising
and lowering operators I+ and I− This hamiltonian contains non-diagonal ma-
trix elements and the energy eigenvalues are altered depending on η. The most
important effect is that the the frequency harmonics are no longer in the ratio
ω1 : ω2 : ω3 = 1 : 2 : 3. They will be related by the expressions,
ω1
η =1− , ω3 = ω1 + ω2
ω2
η is easily measured for a signal in G22 (t). This allows for the identification of
non axially symmetric sites in the studied compound, which is useful in phase
analysis.

3
 fi ωq (Mrad/s) η
.1 60 0
.1 120 0
.1 120 0.02

Table 1: Summary of quadrupole interaction frequencies observed at T=200◦ C.

2.2 Sample Preperation

Samples of In3 Zr were made with high purity In and Zr metals with small
amounts (10−8 mole fraction) of radioactive 111 In. The 111 In was diluted in
1M hydrochloric acid and dried on the In metal. After letting the probe atoms
diffuse into the In metal, In and Zr metals were arc welded under argon gas.
The samples made typically had masses of 50mg.

3 Results
A set of 5 samples of In3 Zr were examined at temperatures ranging from
30◦ C to 700◦ C. Samples also varied in mole fraction of In metal, including
20%, 25%and27% In.