Journal of Magnetism and Magnetic Materials 469 (2019) 178–182

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Journal of Magnetism and Magnetic Materials

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Research articles

The low temperature specific heat of single crystal Er-Al2 compound T

Kadhim A.M. Khalaf
Department of Mathematical and Physical Sciences, College of Arts and Sciences, University of Nizwa, P.O. Box (33), P. Code (616), Oman

A R T I C LE I N FO A B S T R A C T

Keywords: The low temperature heat capacity of the ErAl2 single crystal compound have been measured in the temperature
Rare earth compounds 2– 40 K using a modified adiabatic continues heating technique. The magnetic contributions to the total specific
Magnetic phase transition heat were extracted using similar but nonmagnetic “lattice blank”, which gives a good description of the non-
Low temperature specific heat magnetic contributions to the heat capacities. The magnetic specific heat exhibits large anomaly at the highly
Schottky effect
cooperative magnetic phase transition, which lies at about 12 K. A broad Schottky anomaly was shown centered
Magnetic entropy
at about 30 K. The magnetic contributions to the heat capacity of the ErAl2 compound, Cm(T) have been cal-
Critical exponents
Spin waves culated using mean field approximation. The Hamiltonian has been taken to be the sum of crystal field and
isotropic exchange terms. A computer program based on the molecular field approximation has been written to
calculate the crystal field levels and the magnetic contributions to the heat capacity as a function of temperature
in the ErAl2 compound. The critical exponent analysis showed that α′ ≈ α and A′/A ≈ 1.9. The low temperature
magnetic specific heats behave as T3/2 in support of the spin wave excitations predictions.

1. Introduction 10 T. It was found that the Curie temperature of the (Dy1−xErx)Al2

The REAl2 (RE = rare earth metal) compounds have the cubic Laves
phases (Cu2-Mg)-type structure. These compounds undergo magnetic
phase transition from paramagnetic to the ferromagnetic state at the
Curie temperature TC. The REAl2 intermetallic compounds have inter-
esting magnetic properties and received great attention [1–3]. It is well
known that the crystal field splitting is larger than the exchange in-
teraction in the cubic rare-earth (RE) aluminum (Al) alloys. According
to the effective magnetic moment observed in the high temperature
paramagnetic susceptibility, the rare earths are in the RE3+ state with a
well-defined number of 4f electrons. The magnetic properties of the
ErAl2 compound have been investigated by neutron diffraction. The
magnetic susceptibility measurements showed that this compound has
an effective magnetic moment per molecule in the paramagnetic region
of 9.2μB and it obeys the Curie-Weiss law. The ErAl2 order ferro-
magnetically with Curie temperature 14 K [4]. The heat capacity re-
sults, Cp of the nonmagnetic rare earth compounds YAl2, LaAl2 and
LuAl2 were reported in the temperature range 2·5– 20 K [5]. The low
temperature analysis of these results were obtained from the least
square fittings of the Cp vs. T2 plot yielded values for the electronic
specific heat coefficient, γ = (1·81, 3.65 and 1.90 mJ/mol,K2) and
Debye temperature, θD(0) = (473, 352 and 384 K) for (YAl2, LaAl2 and
LuAl2 compounds) respectively [5]. The low temperature heat capacity
and the magnetic phase diagram of the (Dy1−xErx)Al2 system have been
investigated in the temperature range 3– 350 K in magnetic fields up to
system vary between 65 K for DyAl2 to 13 K for ErAl2 [6]. The heat
capacities of the DyAl2, ErAl2 and LuAl2 compounds were measured in
the temperature range 5– 300 K using adiabatic calorimetry technique.
The specific heats of the DyAl2 and ErAl2 compounds were character-
ized by sharp anomalies at temperatures 58.0 K and 10.2 K respectively,
which were attributed to the magnetic phase transitions. The magnetic
contributions to the total heat capacity have been separated from the
measured heat capacities by subtracting the specific heat of the non-
magnetic LuAl2 compound [7]. The heat capacities of the YbAl2, CaAl2,
EuAl2 and ErAl2 compounds were measured in the temperature 400 K–
1200 K using drop calorimeter technique [8]. The low temperature
specific heats of the ErxY1−x system, where x (=0, 0.03, 0.05, 0.07 and
0.10) have been reported [9]. It was found that the low lying crystalline
electric fields (CEF) in both the ErAl2 [8] and ErxY1−x [9] compounds
give rise to a Schottky heat capacity anomaly centered at about 23 K.
The thermal conductivities of the REAl2 compounds in the temperature
range 4.2 K to room temperature have been analyzed in terms of the
electronic, lattice and magnetic terms [10]. The temperature depen-
dence of the thermoelectric and the electrical resistivity in the tem-
perature range up to 1000 K for all the REAl2 compounds have been
reported [11].
The aims of this paper are to report on experimental measurements
of the low temperature heat capacity of single crystal ErAl2 compound
to estimate the electronic, lattice and magnetic terms and to test the
validity of the mean field approximation approach and the spin waves

E-mail address: kadhimm@unizwa.edu.om.

https://doi.org/10.1016/j.jmmm.2018.08.047
Received 7 May 2018; Received in revised form 27 July 2018; Accepted 18 August 2018
Available online 23 August 2018
0304-8853/ © 2018 Elsevier B.V. All rights reserved.
K.A.M. Khalaf Journal of Magnetism and Magnetic Materials 469 (2019) 178–182

excitations in the predictions of the magnetic specific heat, Cm and its π2 2

Ce (fermions ) = K N
3 B
(EF ) T
variation as T3/2 respectively.
Ce = γ T
(2)
2. Experimental
where KB, N(EF) and γ represent Boltzmann’s factor, the density of
states at Fermi level and electronic specific heat coefficient respec-
A modified adiabatic continuous heating technique has been em-
tively.
ployed to obtain reliable results for the heat capacity of small samples
The lattice specific heat (the phonons) term can be written as;
in the temperature range between liquid helium and liquid nitrogen.
The sample temperature was monitored using a calibrated germanium 3
T θD / T x 4e x
thermometer, GR-200B-1500 supplied by Lake Shore Cryogenics Ltd. A Cl (phonons ) = 9NKB T ⎛ ⎞ ∫ ⎜
x
⎟
2
dx
⎝ D ⎠ 0 (e −1)
θ
digitally controlled heater power supply has been used to meet the
requirements of the automated calorimeter. The calorimeter and where (x = ħω/KBT) and θD and N represent the Debye temperature
sample was first cooled down to less than 2 K by pumping the liquid and the Avogadro number. For low temperatures (T < θD/10) the
helium-4 with the use of the mechanical heat switch arrangements. phonons term can be written as in the following relations;
Running the experiment and data acquisition were done automatically
Cl = β T 3 (3)
by a programmed microcomputer. Details of the experimental techni-
ques have been published elsewhere [12–13]. where β represents the lattice specific heat coefficient. The coefficient,
The sample was a 2.42 g single crystal of ErAl2 supplied by the β is related to Debye temperature, θD(0) through the relations;
Birmingham center for materials research. The experimental heat ca-
3
pacity measurements have been done between 2 and 40 K in two steps; 12Rπ 4⎛
1 ⎞
⎫
⎝ θD (0) ⎠
the first step was the use of the pulse heating calorimetry in the tem- β= 5
⎪
perature range (2– 7 K) and the second step was the use of continuous ⎬
1
heating calorimetry for (4.2– 40 K). The overlapping between the two
regions was very good. In order to ensure good thermal and mechanical
θD (0) = ( )
1944
β
3 ⎪
⎭ (4)
contact between the sample and sample holder one face of the sample
The magnons contributions to the specific heat can be written as;
was spark planed and attached to the copper disc sample holder with
3
the help of the G.E. 7031 varnish. The heat capacities of the sample ∞ 5/2 x
KB ⎛ KB T ⎞ 2
holder addenda and the varnish have been subtracted from the mea- Cm (magnons ) = ⎜ ⎟
4π 2 ⎝ Dstif ⎠
∫ (exx−1)e 2 dx
sured total heat capacity. A computer program has been written to 0

calculate the crystal field levels in the ErAl2 compounds using the where Dstif represent the spin-wave stiffness coefficient. At tempera-
molecular field approximation then calculate the magnetic contribution tures below the Curie temperature, TC, the Cm(magnon) can be written
to the heat capacity [14–15]. as;

Cm = Dstif T 3/2 (5)

3. Results and discussions
The total specific heat results of the ErAl2 sample are presented in
Fig. 1 together with the estimated lattice specific heat in this sample.
The low temperature specific heats of the REAl2 ferromagnetic com-
pounds were analyzed in terms of the electronic, lattice and magnetic
contributions and may be written as [16–17];
Cp = Ce + Cl + Cm
where Ce, Cl and Cm correspond to the electronic, phonon and magnetic
contributions to the total specific heat respectively.
The electronic specific heat Ce can be written as;
The magnetic contribution, Cm to the total heat capacity was ex-
tracted by subtracting the estimated non-magnetic specific heats
(Ce+Cl) in the magnetic REAl2 compounds. The estimation was done by
linear interpolation between heat capacities of the non-magnetic,
Cp(LaAl2) and Cp(LuAl2) compounds made by atomic number.
Therefore, the magnetic specific heat in the ErAl2 compound can be
written as;
(1)
Cm (ErAl2) = Cp (ErAl2 )−Cp (Interp. between LaAl2 & LuAl2) (6)
The estimated lattice heat capacity data were illustrated together
with the raw data in Fig. 1. The extracted magnetic contributions to the
specific heat, Cm versus temperature are shown in Fig. 2. It is clear that
a large anomaly at about 12 K superimposed on a broad Schottky
anomaly centered at about 30 K. The anomaly at 12 K was identified as
a λ-type magnetic phase transition.
The mean field calculations of the magnetic specific heat of the
ErAl2 compound using the mean field approximations can be sum-
marized as follows;
The Hamiltonian, H has been taken to be the sum of crystal field, Hcf
and isotropic exchange terms [14–15]. So that;

H = Hcf − ∑ ∂ij Ji . Jj
ij

Hcf = B4O (O4O + 5O44 ) + B6O (O6O−21O64 )

Fig.1. The total specific heat, Cp and the lattice specific heat, Cl versus tem-
perature for the REAl2 compounds.
where Blm and Olm are the CEF parameters and the Stevens operators
[16] respectively, Ji is the spin on the ith ion and ∂ij is the exchange
integral. Values of the parameters were obtained as B4O = 1.08 × 10−4
and B6O = −1.09 × 10−6 [14]. By ignoring the fluctuations [14–15]
the remaining Hamiltonian can be written as:

179
K.A.M. Khalaf Journal of Magnetism and Magnetic Materials 469 (2019) 178–182

∂〈H 〉 dE1 1
∑ ∂E1 dHmf
=
KT
{ 〈MH 〉−〈M 〉〈H 〉 }
i

where

〈M 〉 =
( )
∑ 〈i|J 2|i〉 exp − KTi
E

( )
∑ exp − KT
Ej

〈MH 〉 =
( )
ΣEj 〈i J 2 i〉 exp − KTi
E

( )
Σ exp − KT
Ej

This will leave the term (dM/dT) to be evaluated. The partial dif-
ferentiation gives the following relation;
∂M
dM
= ∂T
dT 1−λχo

where
Fig.2. The experimental (dots) and predicted (solid line) magnetic specific
∂M
heats versus temperature for the REAl2 compounds. The inset: Magnification of χo =
Cm versus T between 18 K and 38 K. ∂T
and
H = Hcf −2 ∑ ∂ij Ji . Jj + ∑ ∂ij Ji . Jj ∂M 1
ij ij
= { 〈MH 〉−〈M 〉〈H 〉 }
∂T KT 2
The Hamiltonian familiar form can be written as: so that
1
H = Hcf −gμB ∑ J12 Hmf + ⎛ ⎞ λM 2 ∂〈H 〉 dE1 1 λ ⎞
⎝2⎠ ∑ = 2 3 { 〈MH 〉−〈M 〉〈H 〉 }2 ⎜⎛ ⎟
i
i
∂E1 dT K T ⎝ 1−λχo ⎠
The magnetic specific heat is defined as;
Therefore, the heat capacity will be given by;
dU d < H >
Cm = − N 1 ⎛ λ ⎞
dT dT Cv = ⎛ ⎞ ( 〈H 2〉−〈H 2〉 ) + ⎜ ⎟ ( 〈MH 〉−〈M 〉〈H 〉 )
2
⎝ KT 2 ⎠ K 2T 3 ⎝ 1−λχo ⎠ (7)
This is to be evaluated in the paramagnetic regime above the Curie
temperature, where there is zero net magnetization and zero mean Knowing the crystal field parameters allows direct prediction of the
field; i.e. magnetic specific heat. The predicted results are presented in Fig. 2.
dE1 It is clear that the magnetic specific heat exhibits sharp maxima,
=0 which has been identified as a first order λ-type magnetic phase tran-
dT
sition at about 12 K followed by quite broad anomaly centered at about
in this case 30, which might be caused by the Schottky effect, which arises from the
1 repopulation of the crystal field levels. The Schottky effect is very well
Cm = { < H 2 > −< H >2 }
KT 2 known in Er-compounds at low temperatures [8–9]. Other magnetic
effects such as the residual magnetic impurities in the compound might
where
share the cause. The Schottky effect is not clear on the figure because its

<H 2 > =
∑i E12 exp − KT1 ( ) E value is much smaller than the main Cm. In order to magnify the effect
the Cm results have been replotted in the temperature range 18– 38 K
∑j exp − KT ( )
Ej
and shown in the inset of Fig. 2. It is clear that the broad maximum lies
∂ < H > dE1
at about 30 K. Other Er compounds have been reported to show the
In the ferromagnetic region, the term; ∑i ∂E1 dT
must also be same effects at about 23 K [8–9]. The shift in the position of the maxima
dE
differentiated because dT1 ≠ 0 the energy levels are temperature de- might be caused by the short outcomes of the molecular field model.
pendent because the magnetization is a function of temperature. The The limitations of the mean field theory are clearly visible in the shift of
calculation was performed in the following steps. First of all the mo- the position of predicted results from that of the experimental and the
lecular field was differentiated through; shift of the Schottky anomaly position to higher temperatures, but the
overall agreement between the values of the experimental and theore-
∂〈H 〉 dE1 ∂〈H 〉 dE1 dM
∑ ∂E1 dT
= ∑ λ
∂E1 dHmf dT
tical results can be considered to be fairly acceptable for such simple
i i model. This procedure is quite similar to the one followed in the
Since dHmf = λdM at constant temperature. Then the energy levels treatment of the magnetic specific heat of the NdAl2 compounds [15].
can be written as a perturbation expansion in the molecular field, i.e; The magnetic entropy changes, Sm are related to the magnetic
specific heat, Cm(T) through the following relations;
E1 = E1 (0)−E1(1) Hmf −E1(2) Hmf
2
T Cm
Sm (Tm) = ∫0 m T
dT (a) ⎫
where
⎬
Sm (max ) = Rln (2J + 1) (b) ⎭ (8)
E1(1) = < 1 J 2 1>
where R is the gas constant. Therefore, the magnetic entropy changes,
∑ < i J2 i > 2
E1(2) = , Ej ≠ Ei Sm(Tm) in the compound between 0 K and Tm have been determined by
Ej−Ei integrating the smoothed Cm(T) values between 0 K and Tm

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K.A.M. Khalaf Journal of Magnetism and Magnetic Materials 469 (2019) 178–182

Fig.4. The log(Cm) versus log(τ) for T > TC.

Fig.3. The log(Cm) versus log(τ) for T < TC.

These exponents describe the behavior of a function f(τ) in the region of

interest. The parameter τ is known as the reduced temperature
Table 1 (τ = |T − TC|/TC). The target was to estimate the critical exponent α,
Values of critical exponents parameters α and A. which is usually defined as;
Temperature Range 10.4 K–11.6 K 12 K–13.2 K A′/A lnf(τ )
α = lim
τ→0 lnτ (9)
α −0.05 ± 0.03 −0.12 ± 0.02 1.86
A 1.12 2.088 The magnetic specific heat results are usually fitted to an equation
of the following form [17–18];

Cm = ( )τ
A
α
−α +B ⎫
⎪
T − TC ⎬
respectively. Moreover, the maximum magnetic entropy changes, τ= ⎪
TC
⎭ (10)
Sm(max) are theoretically related to the total magnetic spin, J, of the
magnetic element in the magnetic systems through the relation where A and B are constants and τ = |T − Tc|/Tc represents the re-
(8b).The numerically estimated values of the magnetic entropy duced temperature. The scaling hypothesis predicts that α = α′ and
changes, Sm(Tm) between 0 K and Tm are equal to about (14.2 J/mol,K) B = B′, while in general A ≠ A′ in the regions below and above the
[14], while the maximum entropy values obtained for Er ions J = 15/2 critical temperature TC. Thus, a plot of log(Cm) against log(τ) was ex-
are about (17.8 J/mol,K). The ratio of Sm(Tm)/Sm(max) are about pected to be asymptotically linear (asymptotic scaling) with equal
(80 ± 2)%. This indicates that the effective J value is equal to about 9/ slopes for the branches above and below TC. This is a kind of form
2 rather than 15/2 in the compound. expected from the theory of the specific heat of simple Heisenberg
The heat capacities of the ferromagnetic, anti-ferroelectric and su- magnetic ferromagnetic and antiferromagnetic systems [18–19]. It was
perconductor materials were usually analyzed using the critical-point found that fitting the magnetic specific heat results of the ErAl2 com-
exponents as they are characterized by a rather narrow critical region. pounds to Eq. (10) in the critical region does not result in a straight line.

181
K.A.M. Khalaf
(a)
(b)
Fig.5. The spin wave behaviors (a) Cm versus T (b) Cm versus T3/2.
A straight lines have been obtained by plotting the results as log(Cm)
versus log(τ). Fig. 3 shows that straight lines have been obtained in the
temperature range 10.4–11.6 K for (T < Tc) with values of
α ≅ (−0.05 ± 0.03) and A = 1.12. The results are shown in Table 1.
Fig. 4 shows the the Log10(Cm) versus Log10(Tc − T)/Tc) plot for
T > Tc (above the transition temperature TC). The best linear fit for the
high temperature region (T > TC) lies in the range 12 K–13.2 K. The
best value of α′ was found to be (−0.12 ± 0.02) and A′ = 2.088. It is
clear that α′ ≅ α and A′/A ≅ 1.86.
The magnetic contributions to the specific heat in ferromagnetic
materials below their Curie temperatures were usually attributed to the
spin wave excitations, which vary as T3/2. The low temperature results
below 11 K have been reshown in Fig. 5 as a function of T and T3/2. The
behaviors of Cm are fairly satisfying the spin wave predictions [18–19].
4. Conclusions
The low temperature heat capacity of the ErAl2 single crystal
compound has been measured in the temperature 2– 40 K. The mag-
netic term, Cm has been separated from the total term, Cp, by sub-
tracting the nonmagnetic terms, Ce and CL. The magnetic specific heat,
Cm exhibits two main anomalies; firstly, the λ-type phase transition at
about 12 K. Secondly, the Schottky anomaly, which is centered at about
30 K. The numerically estimated value of the magnetic entropy
182
Journal of Magnetism and Magnetic Materials 469 (2019) 178–182
changes, Sm(Tm) between 0 K and 12 K equals to about (14.2 J/mol,K),
which is less than the expected maximum entropy (17.8 J/mol,K) for Er
ions (J = 15/2). This indicates that the effective J value is equal to
about 9/2 rather than 15/2 in the ErAl2 compound. The behaviours of
low temperature magnetic specific heat results below 11 K vary as T3/2
satisfying the spin wave predictions. The critical exponents analysis of
Cm in the vicinity of the λ-point can be summarized as (α′ ≈ α) and (A′/
A ≈ 1.9) in the narrow region below and above TC. The disagreement
between the experimental and predicted results in the vicinity of the λ-
point and the shift of the Schottky anomaly position to higher tem-
peratures have been attributed to the limitations of the predictions of
the mean field theory. In general the overall agreement between the
experimental and theoretical results can be considered as fairly sa-
tisfying for such simple model.
Acknowledgements
The experimental measurements have been done at the Physics
Department, University of Southampton (U.K.). I would like to thank
Prof. B.D. Rainford, Prof. P. C. Lanchester and Dr. H.B. Stanley for their
support and useful discussions.
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