et al.

: Electrical and Thermal Studies of [(NH& _,K,]2S04

S. AHMED 163

phys. stat. sol. (a) 117, 163 (1990)

Subject classification: 64,70; 72,20; S11

Mathematics and Science Department, Faculty of Petroleum and Mining Engineering ( a )

and Physics Department, Faculty of Science ( b ) ,
Suez Canal University, Suez')

Electrical and Thermal Studies

of [(NH4)1-,K,],SO, Crystals at High Temperature
BY
S. AHMED (a), H. A. KHALIK
(a), A. M. SHAMAH (b), A. IBRAHIM (b),
and F. HANNA(a)

DC resistivity measurements as function of temperature and DTA thermograms are used to study the
phase transition above room temperature in [(NH4)1-,K,],SO, crystals with x = 0.0, 0.15, 0.25, and
0.325. It is confirmed that there is a phase transition at 423,463,488, and 517 K for crystals with x = 0.0,
0.15, 0.25, and 0.325, respectively. The resistivity data fall into two straight regions showing that more
than one defect mechanism is involved in the conduction process. The cationic and anionic impurities
contribute the main part of conduction process in the lower region. At the transition temperatures the
resistivity changes due to the generation of a large number of protonic defects. Activation energies for
[(NH4)' -,K,],SO, crystals as function of the K ion concentration are presented.
+

Gleichspannungsleitfahigkeitsmessungen in Abhangigkeit von der Temperatur und DTA-Thermo-

gramme werden benutzt, um den Phaseniibergang oberhalb Zimmertemperatur in [(NH,)' -xK,],S04-
Kristallen rnit x = 0,O; 0,15; 0,25 und 0,325 zu untersuchen. Es wird bestatigt, daB ein Phaseniibergang
bei 423,463,488 und 517 K fur Kristalle mit x = 0,O; 0,15; 0,25 bzw. 0,325 existiert. Die Leitfahigkeits-
werte zerfallen in zwei Bereiche und zeigen, dal3 mehr als ein Defektmechanismus am Leitungsprinzip
beteiligt ist. Die Kationen- und Anionen-Storstellen tragen den Hauptanteil des Leitungsprozesses im
niedrigen Bereich. Bei der Ubcrgangstemperatur andert sich die Leitfiihigkeit infolge der Generation
einer grol3en Zahl von Protonendefekten. Aktivierungsenergien fur [(NH4)' _xK,],S04-Kristalle als
Funktion der K+-Ionen-Konzentrdtionen werden angegeben.

1. Introduction

[(NH4),~.KX],SO4 powdered crystals with x = 0.0, 0.1, 0.25, 0.32, 0.6, 0.7, and 1.0 have
been studied previously by X-ray diffraction and dielectric constant measurements from
room temperature down to 73 K [1,2]. It has been found that the addition of potassium
ions to ammonium sulphate alters its properties: the unit cell volume decreases, the dielectric
constant is lowered, and the transition temperature decreases. It was also noticed that there
is no phase transition for x > 0.6.
Using X-ray diffraction we studied [3] ammonium sulphate crystals throughout the
paraelectric region from room temperature up to the dissociation point, where we confirmed
the presence of a phase transition in this high temperature region at nearly 423 K.
Accordingly it is interesting to study the effect of doping (NH4),S04 crystals by K f ions
on the different properties of (NH,),SO, in the paraelectric region above room temperature.
The study might also help in understanding the mechanism of the high temperature phase

I) Suez, Egypt.

I I*
164 H.A. KHALIK,A. IBRAHIM,and F. HANNA
S. AHMED,A. M. SHAMAH,

transition. It is hoped to throw more light on the role played by NH: ions in the transition
in order to present a reasonable theoretical model describing fully the origin of the phase
transition concerned.

2. Experiments
Two types of experiments have been made, namely, direct current resistivity measurements
at different temperatures (from room temperature up to the dissociation point) and
differential thermal analysis (DTA).

2.1 Sample preparation

Both (NH4),SO, and K 2 S 0 4 have been obtained from British Drug Houses (London) and
used in the preparation of the [(NHJ1 -,K,],SO, series with x = 0.15,0.25, and 0.325 by the
same method which has been reported before [l, 21.
The samples used for the dc resistivity measurements were prepared by compressing the
powder in the form of disks by hydraulic pressure. A silver paste solution was spread as a
thin film on the opposite faces of the disk to form electrical silver electrodes.

2.2 dc resistivity and DTA measurements

The dc resistivity for polycrystalline samples of pure (NH,),SO, and [(NH4)1-,K,],SO,
crystals with x = 0.15,0.25,0.325 were measured over a wide temperature range from room
temperature up to nearly the dissociation point of each sample. The experimental
measurement of the temperature dependence of edCfor the test samples were repeated on
several samples (four at least), and the experimental runs were also repeated several times
for each sample. Data obtained for different samples and different runs showed good
reproducibility. It was found that the characteristic behaviour of the dc resistance is affected
by the heating rate of the test samples. In our measurements the heating rate was about
2 K/min, however, near the transition temperature a slower heating rate of 0.2 K/min was
affected to attain better results. In addition, each of the samples was first annealed at 373 K
for 2 h to avoid surface conduction.
Differential thermal analysis (DTA) was performed on all the test samples under
atmospheric pressure from room temperature up to the dissociation point of each sample.
To attain better DTA thermograms, a series of DTA runs have been made for each
sample under different conditions, i.e., rate of heating and sensitivity, and the best DTA
thermograms are presented.

3. Results, Analysis and Discussion

3.1 dc resistivity
As mentioned above the resistivity as a function of temperature has been measured for
each sample. In edChas been plotted (Fig. 1) as a function of the reciprocal temperature for
[NH4)1-rKx]2SOScrystals with x = 0.0, 0.15, 0.25, and 0.325. For (NH,),SO, crystals
Fig. 1, curve a shows two distinct linear parts, characterizing the ionic crystals, with two
remarkable bends at 413 and 423 K. The first bend might be related to the onset of the phase
transition and the second to the T, (423 K) of this transformation. This suggested a phase
transition at 423 K for (NH,),SO, which agrees with Symaprased and Vallabhan [4], and
disagrees with Hugo Schmidt [5].
Electrical and Thermal Studies of [(NH,), -,K,],SO, at High Temperature 165

Y.' ' ' ' ' ' ' ' ' ' 7Fig. 1. Direct current resistivity (In ed,) of [NHJ, -xKx]2
'SO, crystals as a function of temperature during heating
17
:of the samples

15
The same observation might be seen from Fig. 1 for
the mixed crystals [(NHJ1 -xKx],S04 with x = 0.15,
0.23, and 0.325, namely, each crystal suffers a phase
transition at a certain temperature above room
17 temperature. Fig. 1 indicates also that the transition
C
1
temperature systematically increases with increasing
x. Also the type of the transition changes from a
continuous to a discontinuous type, i.e. from second
13 order to close to first order at the critical concentra-
19 tion of x = 0.325.
The activation energy for each sample has been
17 calculated from Fig. 1 and is shown in Table 1, which
indicates that E increases as K content increase.
+

3.2 Differential thermal analysis ( D T A )

13 Fig. 2 (curve a) represents the DTA thermogram for
4
19 - pure (NH,),SO,. The figure shows that a broad
0.325 1 endothermic weak peak corresponding to an endo-
1 thermic phase transition of second-order type took
I place at about 423 K.
- The DTA curves of the mixed crystal samples
1 [NH,), -xK,],SO, with x = 0.15,0.25, and 0.325 are
Z shown in Fig. 2. The figure shows that the presence
'' 26 ''
; of the K + ion changes systematically the transition
temperature, and also the rate of the phase transition.
?03(K-1) -.---- When x increases the transition temperature in-
creases and the order of the phase transition de-
creases.
The above results obtained from both dc resistivity measurements and DTA thermograms
are in good agreement.

Table 1
Activation energies for [NHJ1 -,K,],SO, crystals as a function of K'ion concentration

X E(eV)
lower region higher region

0 0.23 1.17
0.15 0.64 1.36
0.25 0.82 1.45
0.325 1.08 1.70
166 H. A. KHALIK,
S. AHMED,A. M. SHAMAH, and F. HANNA
A. IBRAHIM,

Fig. 2 Differential thermal analysis (DTA) thermograms

of [(NH4)1-xK,],S04 crystals during heating of the

333 373 413 453 493

T(NI - 533

4. Discussion and Conclusion

From both previous and present studies a second-order phase transition at 423 K
(paraelectric region) for (NH,),S04 crystals has been confirmed which is not of a structural
type.
As has been shown in Section 3, [(NH4),-xK,]2S0, crystals with x = 0.15, 0.25, and
0.325 suffer a phase transition at certain temperature above room temperature with the same
features as that for (NH,),SO, crystals. It was found that the addition of K C ions to
(NH,),SO, increases the transition temperature and changes the order of the phase
transformation from second order to first order.
The observed two straight regions in the resistivity for [(NH4)1-,K,],SO, crystals
suggested that more than one defect mechanism is involved in the conduction process. To
understand the mechanism of conduction in such ionic crystals, one has to remember that
in ionic crystals containing ammonium groups, e.g. NH,CI, NH,HSO,, and LiNH,SO,,
the point defects are ionic, electronic (electrons and holes), and protonic [6 to 81, i.e.
conductivity may be ionic, electronic, and protonic. Unlike typical ionic crystals, (NH4),SO4
has the two ions NH: and SO:- of large size (low mobility), hence they play a small part
in the conduction process in the lower region. So the cationic and anionic impurities might
play the main part in the conduction process.
The electrical conductivity studies in ammonium containing crystals such as NH,C1 [6]
and NH,Br [9], (NH,),SO, [4], LiNH,S04 [8], and (NH,),H(SO,), [lo] revealed that the
reorientation of free rotation effects of the NH, groups in these crystals can lead to phase
transition. Such rotational motion of the NH: ions causes a weaking effect on the ion
bonds. Hence the NHf ions in (NH,),SO, might cause the generation of large number of
protonic defects giving rise to an increase in conductivity and a phase transition of this
type. Our present studies of the temperature dependence of e, DTA thermograms, and
lattice constants [3] of the (NH,),SO, crystal confirmed that such a transition of the above
type occured at 423 K in (NH,),SO, associated with an increase in conductivity due to
Electrical and Thermal Studies of [(NH,), _,K,],SO, at High Temperature 167

the generation of a large number of protonic defects at the transition temperature (Fig. 1,2).
The observed phase transformation of (NH,),SO, at 423 K was found to be very sensitive
to the replacement parameter (s)(Fig. 1,2). The presence of K + ions reduces systematically
the dc resistivity of (NH,),SO,. Since r(K+) = 0.133 nm is less than u(NHf) = 0.t43 nm
the conductivity might due to the migration of interstitial K' ions.
On the other hand, from the nature of the structural changes with temperature occurring
in the crystals K,SO, [ l l ] and K,SeO, [12] which are isomorphous with (NH,),SO,, it
was inferred that SO:- ions played a role in all the anomolous behaviour of these crystals.
From the above analysis one might conclude that in (NH,),SO, each of the three
molecular groups present in the crystal, [NH: (I), NH; (II), and SO, ions] plays a part in
the phase transition process occurring in (NH,),SO, at 423 K. But the main part might be
due to the motion of ammonium ions where the transition of (NH,),SO, at 423 K can be
attributed to the onset of free rotation of the NHf ions. In addition the increase of a large
number of protonic defects generated due to the unrestricted rotation of the NH; ions leads
to the low temperature resistivity anomaly.

References
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(Received June 19, 1989; in reaisedforrn November I , 1989)