Journal of the Korean Physical Society, Vol. 32, February 1998, pp.

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Thermal and Dielectric Studies of Protonated Potassium Phosphate Glass

Hideki Obara, Osamu Yamamuro and Takasuke Matsuo
Department of Chemistry and Microcalorimetry Research Center, Graduate School of Science
Osaka University, Osaka 560, Japan
Several protonated glassy potassium phosphate samples were prepared from molten KH2 PO4 by
rapid cooling. The average composition was KH1.34 PO3.67 . The crystalline samples were obtained
by annealing the glass at ca. 430 K. The heat capacities and dielectric permittivities were measured.
In the glassy sample, a glass transition appeared at 323 K. The crystalline sample underwent a
lambda phase transition at 157 K. The permittivity of the glassy sample decreased with decreasing
temperature with a larger temperature coefficient below 20 K. The heat capacity difference between
glassy and crystalline samples was reproduced by the Schottky heat capacity with = 40 cm1 .

I. INTRODUCTION
Organic and inorganic polymers and certain types of
low molecular weight substances vitrify into amorphous
solids when cooled from the melt. The capability of
these materials to circumvent crystallization depend on,
among other things, the chemical bonding by which the
molecules are connected. Directional bonds such as those
in synthetic polymers, quartz and glycerol facilitate glass
formation. In KH2 PO4 the hydrogen bond combining
neighboring phosphate ions is directional and thus is a favorable factor for vitrification. This compound has been
amorphized by application of high pressure [1] as are ice
[2] and quartz [3]. However, there has been no report
in the literature describing vitrification of KH2 PO4 from
the melt [4]. In the study presented here, we prepared a
partially dehydrated glassy form of KH2 PO4 and examined its thermal and dielectric properties.

dehydration. The crystalline samples, probably a mixture of phases, were obtained by annealing the glass at
ca. 430 K for 12 hours. Figure shows the X-ray diffraction patterns of the glassy and crystalline samples. It
shows that the vitrification and the crystallization were
complete.

2. Heat Capacity Measurements

The heat capacities of glassy KH1.34 PO3.67 and crystalline KH1.34 PO3.67 were measured with an adiabatic
calorimeter in the temperature range between 7 and
350 K and between 12 and 350 K, respectively. The
masses of the glassy and crystalline KH1.34 PO3.67 samples used were 5.65762 g and 5.54707 g, respectively. The
samples were sealed in a calorimetric sample cell together
with He gas at atmosphere pressure at 300 K for rapid
thermal conduction in the cell.

II. EXPERIMENTAL
3. Dielectric Measurements

1. Sample Preparation

Commercial crystals of KH2 PO4 were melted in a silicate glass ampule, poured onto a plate of copper and immediately press-cooled with another plate of copper into
a transparent slab of glassy potassium hydrogen phosphate. Thermogravimetry gave the average composition
of the partially dehydrated phosphate as KH1.34 PO3.67
from the loss of the sample mass upon heating to full

Contribution No. 134 from the Microcalorimetry Research

Center.

The dielectric permittivities of glassy and crystalline

KH1.36 PO3.68 were measured in the temperature range
between 6 and 300 K with an LCR meter (HP model
4284A) at frequencies 1 kHz, 10 kHz and 100 kHz. The
sample was placed in a doubly thermostated space in a
cryostat. The sample space in the cryostat was filled
with an appropriate pressure (10 kPa) of He gas to
attain homogeneous temperature control. The samples
were shaped and polished with abrasive paper to form a
disk of 17.15 mm in diameter and 1.700 mm in thickness
for the glass and 17.60 mm in diameter and 1.685 mm in

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Journal of the Korean Physical Society, Vol. 32, February 1998

Fig.
1.
The X-ray diffraction patterns of glassy
KH1.36 PO3.68 () and crystalline KH1.36 PO3.68 (solid line).

Fig. 3. The difference between the heat capacities of glassy

and crystalline KH1.36 PO3.68 () compared with a Schottky
function (solid line).

1. Heat Capacity

thickness for the crystal. The sample faces were coated

with graphite electrodes.

III. RESULTS AND DISCUSSION

Fig. 2. The heat capacity curves of glassy KH1.34 PO3.67

() and crystalline KH1.34 PO3.67 ().

Figure shows the heat capacity curves of the glassy

and crystalline KH1.34 PO3.67 . The ferroelectric transition at 123 K has completely disappeared. A glass transition occurred at 323 K. The strong increase of the heat
capacity at this temperature indicates that the molten

Fig. 4. The dielectric permittivity of glassy KH1.36 PO3.68 .

Thermal and Dielectric Studies of Protonated Potassium Phosphate Glass Hideki Obaraet al

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between the Schottky heat capacity function and the difference between two Einstein functions.

2. The Permittivity

Fig.
5.
The dielectric permittivity of crystalline
KH1.36 PO3.68 .

KH1.34 PO3.67 is fragile in Angells classification [5]. In

the crystalline KH1.34 PO3.67 , one notices the complete
absence of the glass transition at 323 K indicating that
the sample has been fully crystallized. There is a gradual
anomaly at 157 K for the crystalline KH1.34 PO3.67 due
to a phase transition. The transition entropy was determined from the excess heat capacity to be 2.16 JK1
(mol of K+ )1 . The transition temperature is different
from the Curie temperature 123 K of the original material KH2 PO4 . The phase that gives rise to this anomaly
has not been identified.
Apart from this broad peak, the heat capacities of the
two samples are close to each other. However, upon detailed examination, one finds that the heat capacity of
glassy KH1.34 PO3.67 is substantially larger than that of
crystalline KH1.34 PO3.67 at low temperature. The difference was reproduced well by the Schottky heat capacity
function with the excitation energy of 40 cm1 (The comparison at higher temperatures (T > 50 K) is hindered
by the gradual transition.) (Fig. ). This may indicate
that there are more or less isolated pairs of energy levels,
40 cm1 apart, in the glassy sample. Alternatively, this
may indicate that there is a large excess phonon density
of states at 40 cm1 and a deficient state density around
80 cm1 for the glassy sample relative to the crystalline
sample. This interpretation of the fitting presented in
Fig. 3 arises from the mathematical relation that holds

Figures and shows the real part of the permittivity of

glassy and crystalline KH1.36 PO3.68 at 10 kHz, respectively. The results at other frequencies were essentially
the same. The permittivity of the crystalline sample
increased rapidly between 100 and 170 K as the phase
transition was approached from below. Above 170 K, it
remained constant. The temperature dependence of the
permittivity was entirely different from that of KH2 PO4 .
In particular, the permittivity did not obey the CurieWeiss law: the recrystallized material is not ferroelectric.
The permittivity of the glassy sample increased gradually as the temperature increased. The absolute value
of the permittivity of the crystalline sample was much
larger than that of the glassy sample. For KPO3 , the
crystalline sample has a smaller permittivity than the
glassy sample [6]. This indicates that the amorphous
phase is more loosely packed than the crystalline phase
so that it polarized in an electric field more easily than
the crystal. The present result opposing this expectation
may indicate that there is a cooperative effect in the crystalline phase that assists polarization, even though the
cooperativity is not strong enough to produce ferroelectricity.
The permittivities of both samples were linear to 6 K.
On a general basis of thermodynamics, we expect the
permittivity to be independent of temperature near 0 K.
For the glassy sample, the structural disorder allows it to
have a mechanism to disobey the third law. The origin
of the linear temperature dependence for the crystalline
sample has yet to be understood.
ACKNOWLEDGMENTS
We thank Prof. K. Tashiro and Mr. Y. Maeda for
their help with the X-ray diffraction experiment.
REFERENCES
[1] Y. Kobayashi, S. Endo, K. Koto, T. Kikegawa and O.
Shimomura, Phys. Rev. B 51, 9302 (1995).
[2] O. Mishima, L. D. Calvert and E. Whalley, Nature 310,
393 (1984).
[3] R. J. Hemley, A. P. Jephcoat, H. K. Mao, L. C. Ming and
M. H. Manghnani, Nature 334, 52 (1988).
[4] H. Rawson, Inorganic Glass-Forming Systems (Academic
Press, 1967).
[5] C. A. Angell, J. Non-Cryst. Solids 131-133, 13 (1991).
[6] H. Obara, O. Yamamuro and T. Matsuo, unpublished.