S. A. AHMED M. H.

ALI:Electrical and Thermal Studies of NaNO2 and

phys. stat. sol. (b) 194, 517 (1996) Subject classification: 64.60 and 77.80; S1l.l

517

Department of Mathematics and Science; Faculty of Petroleum and Mining Enginee~ing, Suez Canal University, Suez) (a) and Department of Physics, Faculty of Science, Ain Shams University, Cairo ( b )

Electrical and Thermal Studies of NaN02

B Y

S. A. AHMED and M. H. ALI (b)) (a)

(Receiiied May 12, 1995)
The present paper reports on experimental results on polycrystalline NaNO2 employing the dc resistivity, DTA, arid unit cell parameters (measured by X-ray diffractometry) in the temperature range from 298 to 480K. All the presented results confirm, in addition to the well-known phase transitions a t 436.5 and 438 K, the existence of a second-order phase transition occurring at 448 K. We found clear evidences that the ferroelectric phase transition of NaNO2 is of second order close to the first-order one, and the rotation of the NO, radical mostly takes place around the c-axis. The high-temperature phase transformation occurring at 448 K is thought to be due to the completely disordered arrangement of the NO, radicals in the normal paraelectric phase.

1. Introduction
Ferroelectric activity was found in sodium nitrite (NaN02) by Sawada et al. in 1958 [l]. Since then, a considerable amount of experimental and theoretical work has been carried out on the ordered and disordered phases owing to its peculiarity as to the dielectric [l to 31, spectroscopic [4 to 111, and structural [ l a to 151 properties over a wide range of temper at ures . The sodium nitrite crystal undergoes two successive phase transitions, from the disordered paraelectric to the ordered incommensurate phase at TNM 438 K and then to the commensurate ferroelectric phase at TCRZ 436.5 K [16 to 181. The unit cell in the ferroelectric phase is identical with that in the paraelectric phase and contains two formula units in both phases. The crystal is of body-centred orthorhombic structure, the space [20 group is C?:-Im2m [19] in the ferroelectric phase and D ~ ~ - I m m m to 221 in the paraelectric one. The ferroelectricity of NaNO2 is due to the permanent dipoles of the NO; radicals which in the ferroelectric phase are aligned parallel to the spontaneous polarization along the &axis. In the paraelectric phase the NO; radicals point to the fb-directions, i.e. a mirror plane perpendicular to the baxis appears [17, 221. Thc narrow interniediate phase was first reported by Tanisaki [13, 161. Yamada et al. [17] have proposed that this phase is a. kind of antiferroelectric with a sinusoidal modulation of the electric moments of the NO; radicals [23]. The average order of NO; radicals in the b c plane
~~ ~~~

Suez, Egypt. ) Present address: Department of Physics, Tabiik Teachers College, P.O. Box 1144, Tabllk, Saudi Arabia.
I)

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S. A . AHMED M. H. ALI and

varies along the a-axis. The modulation period changes with temperature from 8.4a at TNto 1 0 . 3 ~ TC [24]. at Although the phase transitions in NaNOz have been intensively studied, there are many contrary statements in the literature. For example, some authors have found additional anomalies at 373 [25] and 451 K [lS, 26 to 281. Some authors reported that the character of the NaN02 phase transition at the Curie point is close to the second-order kind [29 to 311 and not of the first-order one a h reported by others [17, 26, 271. Also, although it is well established that the phase transitions are caused by the orientational order-disorder transition of NO; radicals. the rotational axis of the polarization reversal mechanism is not yet sufficiently clear. Some authors reported that the rotation of the NO; radicals takes place around the c-axis [7, 14, 15, 20, 321 while others reported it around the a-axis [9 to 111. To account for the above contradictions in the reported results we studied the temperature behaviour of dc resistivity, differential thermal analysis (DTA), and lattice parameters of the NaNOz crystals.

2. Experiments
The powder sample of sodium nitrite (NaN02) in the present study was obtained from British Drug Houses, Ltd. (London) and had a specified purity of 99.99%. It was purified by recrystallization, dried, crushed, and finally filtered through a 44 ym sieve to give fairly uniform particle size. The samples used for the study of dc resistivity (ed,) were prepared by compressing the test powder sample in the form of pellets of diameter 13 mm and thickness 10 mm by using hydraulic pressure. A silver paste was painted on the opposite faces of the pellet as electrodes. The resistivity data were obtained on raising the temperature from room temperature to 480 K and also on cooling. The sample was heated firstly to about 380 K for 2 h before taking observations to avoid surface conduction. The temperature of the sample was measured by a digital thermometer (type Crisori 637) provided with a Pt thermocouple of accuracy 1 0 . 1 K. The rate of temperature change was about 0.2 K/ min in the vicinity of the transition points and 2 K/min in the other regions. The dc resistance was measured by two methods: directly with a digital multimeter (type Keithley 177) ranged from 2 0 Q to 20MR and using a conventional circuit. Values of edc obtained from the two methods are in good agreement. The experimental runs were carried out on a group of samples and repeated several times for each sample to ensure reproducibility. The measurements of a high-sensitive differential thermal analysis (DTA) were carried out at atniospheric pressure using a DTA30 system (type Shimadzu, Japan). A series of DTA runs have been made under different conditions and the best DTA thermogram is presented on heating and cooling. A high-precision X-ray diffractometer (type Philips P W 1050) attached to a small heating device was used in our investigation for the precise determination of lattice parameters (with a relative accuracy of rim). All measurements were performed on heating over a temperature range of 298 to 480 K. X-ray CuKa radiation (2 = 0.1542 nm) monochromatized by a graphite crystal was used. A range of scattering angles 15" < 20 < 80" was covered in 0.02" steps (A20) with a pre-set time of 20 s per step in the step mode operation.

Electrical and Thermal Studies of NaNO:!

519

3. Results and Discussion

The temperature variation of the dc resistivity in the vicinity of the transition temperatures, as given in Fig. 1, shows slight anomalies at 438 and 448 K in addition to the expected one corresponding to the well-known ferroelectric-incommensurate phase transition temperature at 436.5 K. The data presently obtained for the natural logarithm of dc resistivity (In Qdr) as a function of 1/T are shown in Fig. 2. Except in the vicinity of the transition points (from 432 to 438 K), the exponential law e = P o exp (UIlcT) is obeyed in three distinct regions labelled I, 11, and I11 in Fig. 2 starting from the low-temperature end. Accordingly, anomalous behaviour of Qdr appeared as a change in the slopes of the different regions (Fig. 2). Anyway, it is impossible to decide whether the relation 4 = eo exp ( U / k T ) holds or not in the sinusoidal phase because of the extremely narrow temperature range (about 1 K) of this phase. On the other hand, there is no temperature hysteresis at T since c the heating and cooling curves coincide. The activation energies for conduction obtained from the slopes of the three linear regions I, 11, and I11 are 1.22, 2.07, and 1.64 eV, respectively. Data from literature and the present ones are compared in Table 1. It can be noted that our values are in relatively good agreement with the values of Takagi and Gesi [30]. Fig. 3 shows the DTA thermogram obtained for NaN02. The thermogram indicates that the endothermic phase transition of NaN02 takes place at 437 K while heating but in cooling the reversibility of the exothermic transformation appeared at 436 K. A steplike anomaly is clearly shown at 448 K in the DTA thermogram. On the other hand, we did not find any appreciable change corresponding to the incommensurate-paraelectric transformation at 438 K by the DTA technique.

'428

432

436

440

444

448

452

TIK)
Fig. 1. Temperature dependence of dc resistivity for N a N 0 2 in the vicinity of the transition points

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S. A. AHMED M. H. ALI and

Fig. 2. Temperature dependence of the logarithmic resistivity for NaNOz

2.10

2.18

2.26

2.34

i F2

I 00 o T ( K- I
The lattice parameters and subsequently the unit cell volume of NaN02 were obtained from the accurate measurements of the Bragg angles of at least six well-resolved special ( h O O ) , (OkO), and (001) reflections at room temperature and as functions of temperature. The obtained lattice parameters of the NaNOa crystal at room temperature (298 K) are: a = 0.3569 nm, b = 0.5569 nm, and c = 0.5384 nm in good agreement with t.hose previously reported [19]: a = 0.3560 nm, b = 0.5563 nm, and c = 0.5384 nm. Variations of the lattice parameters a , b, c arid unit cell volume V are shown in Fig. 4 and 5, respectively. It can be seen that a, b, arid V increase with increasing temperature up to 423 K, then decrease with increasing temperature in the temperature range of 9 K just below Tc. On the other hand, as is shown in Fig. 4, the length of the c-axis decreases moderately with increasing temperature up to 432 K , followed by a continuous decrease up to 436 K. Also similar small anomalies in the NaN02 unit cell parameters a, b, c , and V are clearly shown at 448 K. Plots of ed, versus T and 1nedcversus 1/T, given in Fig. 1 and 2, show three anomalies at 436.5, 438, and 448 K. The temperature indicated by the first anomaly corresponds to the well-known transition point TC where the spontaneous polarization disappears [33], the second one at 438 K corresponds to the incommensurate-paraelectric phase point T N ,and the last one at 448 K corresponds to a highest-temperature phase transi-

Electrical and Thermal Studies of NaNOz Table 1 Activation energies (in eV) region I 1.05 1.43 1.22 region I1
-

521

region I11 1.23 3.10 1.64

ref.
~~~

1.39

2.07

1301 r331 present study

tion. The transition point at 448 K, observed in the present study, is somewhat lower than reported in previous works [26, 271. The high-temperature anomaly at 448 K, supported by similar anomalies in DTA, lattice parameters, and unit cell volume, confirms the presence of a second-order phase transition occurring at this temperature. Yamada et al. [17] have measured the temperature dependence of the X-ray diffraction intensity. They reported that the satellite peaks completely disappear from the diffraction patterns = at a critical temperature (Tcr 453 K) and concluded that the NO, radicals can be regarded as completely disordered and NaNOz being paraelectric above 453 K. The anomaly observed here at 448 K confirmed the above conclusion about the existence of such a high critical point at which the disorder of the NO; radicals is completed. The activation energy of the charge transport obtained from the lned, versus l/T curve amounts to 1.22, 2.07, and 1.64 eV in regions I, 11, and 111, respectively. The rate of variation of conductivity CI is higher in region I1 (from T = 438 to 448 K) than in the other two regions. This might be related to the fact that the concentration of anions in region I1 is less than in the other two reT = 4 36 K , gions. The conductivity (5 depends on the I charge transfer and the mean distance moved by the cations before recombining with a nearest nitrite ion. Hence, the recornbination probability in region I1 should be higher. On the other hand, the complete disordering of the NO, radicals, occurring at the critical temperature (T = 448 K) causes a loosening of the ionic bonds [34]. This effect tends to reduce the height of the energy barrier. The reduction of the height of the energy barriers leads to an increasing mobility of the cations, giving rise to the observed increase in conductivity at 448 K.

T,=437 K
Fig. 3. Differential thermal analysis (DTA) thermogram for the NaNOz crystal during a) heating and b) cooling

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S. A. AHUED and M. H. ALI

Fig. 4. Ternperature dependence of the lattice constants a , b, and c for the NaNOl crystal

0.565
h

E 0.561

The linear thermal expansions along the a-, h-, and c-axes show anomalies in the vicinity of Tc with continuous hehaviour in the temperature range of about 9 K below Tc. This fact suggests t,hat the phase transition occurring at Tc is of second order near to the first-order one. The ferroelectric-incommensurate phase transition at Tc is accompanied by contractlions along the a-, b-, and c-axes and of the unit cell volume. The contraction starts at 423 K and reaches its rriaxirriurri at 436 K. The temperature indicated a t the beginning of the contractioris is thought to be related to the onset, of a process 436 K correinvolving orieritational disorder of the NO, radicals, while the other one at,

1101
m I E

rn
I

z >
lTc=436.5
I I ,
I

280

320

360 400 T(K)

440

480

Fig. 5 . Temperature dcpendence of the unit cell volume for the N a N 0 2 crystal

Elwtrical and Thermal Stiidies of NaNOz

523

sporids to the Ciirie temperature (Tc). An explanation of the volume contraction of the NaNOz crystal in the vicinity of the Curie point may be obtained qualitatively by consideration of the change in covalent bond distance when the NO, radical in the fully polarized lattice is misoriented. On the other hand, the enhanced rotation of electric dipoles associated with NO; radicals is expected to increase the expansion coefficients of the lattice parameters. This assumption was confirmed from the sudden expansion in the lattice parameters a , b arid unit cell volume V of NaN02 above Tc. The anomalies observed here for the first time in the unit cell volume at 448 K corifirnied the conclusion about the existence of a critical temperature (Tc,.)at this point. On the other hand, the expansion was not observed in the c-direction above Tc. This might confirm the conclusion that the rotation of NO, radicals takes place around the c-axis. There is no t,emperature hysteresis at Tc on heating arid cooling in the resistivity measurements. On the other hand, in DTA, the ferroelectric-incommensurate transition points (Tc) are 437 and 436 K during heating and cooling, respectively, indicating a temperature hysteresis of about 1 K around Tc. The small temperature hysteresis observed only in DTA on heating and cooling is thought to be related to t,he poor accuracy of the digital temperature display provided with the DTA3O (51K). Accordingly, there is no remarkable temperature hysteresis as observed in the order-disorder phase transition of first order [18] in this material. Again this result clearly shows that, the phase transition at Tc is of second order near to the first-order one. The mean value of the ferroelectric-incommensurate point (Tc) judged from Fig. 1 to 5 is 436.5 K and is in good agreement with the previously reported one.

4. Conclusions
On the basis of the present results of electrical and thermal studies on NaN02 one might conclude the following points: 1. The unit cell parameters at room temperature (ferroe1ect)ric phase) are: n = 0.3569 nm: b = 0.5569 nm, and c = 0.5384 nni. 2. The ferroelectric-incommensurate phase transition at the Ciirie point was fourid to be of second order close to the first-order one. The Curie temperature Tc was deterniined as 436.5 K. The incommensurate-paraelectric transition point was also determined as 438 K. 3. The results of the temperature dependence of dc resistivity and lattice parameters confirmed the existence of the highest-temperature phase transition at 448 K. The highest phase transition point was also checked by DTA. The phase transformation at 448 K in NaNOz is thought to be of second order. 4. Above 448 K, the NO, radicals probably take the completely disordered arrangement in the paraelectric phase. 5. R.otation of NO; radicals niostly takes place around the c-axis.

Acknowledgements The X-ray diffraction experiments were carried out at the Pliysics Department of Sheffield University (England). The authors wish to thank Dr. N. Cowlarn for his generous help throughout the course of this study.

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S. A. AHMED M. H. AM: Electrical and Thermal Studies of NaN02 and

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