Phase Transformations of Rare Earth Sesquioxides La203,

Nd203, Pr2O3 and &o3

BY P. N. MEHROTRA," G. V. CHANDRASHEKAR,* C. N. R. RAO * AND
E. C. SUBBARAO~
The C formof La203 has been prepared and its transformation to the A form is found to take
place at -590C. The C+A transformation of Nd2O3 takes place at 550C. The temperatures
as well as the energies of activation of the phase transformations of the rare earth sesquioxides vary
with the size of the cation. Y2O3undergoes a reversible phase transformation in the temperature
range 400-900C. The phase transformation of La2O3, Nd2O3and Pr203 have been followed by
electrical conductivity measurements. Presence of water vapour lowers the activation energy for
the conduction process as well as the temperature of transformation.
Rare earth sesquioxides exist in the cubic (0, hexagonal ( A) or monoclinic (B)
forms.1 The C form is a defect structure where the metal ion has MO6V2 co-ordination
where V stands for a vacancy along the body diagonal. The A and B forms are
essentially close-packed structures with M07 co-ordination and with the oxide ion
arrangement almost the same as in the fluorite lattice of the rare earth dioxides.
The rare earth sesquioxides from cerium to dysprosium show irreversible crystal
structure transformations from the C to the A or B form, while the sesquioxides of
holmium to lutecium exist only in the C form.2-4 In the present investigation the
phase transformations of some of the rare earth sesquioxides, on which little or no
information is available, have been studied. These studies are of value since many
of these oxides are of importance as ceramic or solid state materials.
EXPERI MENTAL
C-Pr2O3 was prepared by the method reported earlier.4 Y(OH)3, Nd(OW3 and La(OH)3
were prepared by addition of hot ammonium hydroxide solution to the boiling solutions
of the rare earth chlorides or nitrates. Yttrium oxalate was prepared by the addition of
oxalic acid solution to a solution of the nitrate, while yttrium carbonate was prepared by
the addition of sodium bicarbonate solution to a solution of the chloride. La(OH)3 was
decomposed under vacuum (-10-5 torr) at -400'C for about 4 h. X-ray examination
showed the resulting oxide to be amorphous.
The differential thermal analysis (DTA) curves were obtained by employing an Aminco
Thermoanalyzer fitted with an automatic voltage stabilizer, recorder and an amplifier.
The approximate energies E, of activation of the transformation were estimated by the method
of Borchardt and Daniels.5 Good linear plots of log k against 1/T are obtained if the
transformations follow the first-order rate law.
X-ray powder patterns were obtained with a G.E. unit employing a 114.6 mm camera.
Copper Ka radiation was used. The X-ray diffraction patterns of Y2Q3 were obtained in
the range 25-1 100C employing a G.E. X-ray diffractometer fitted with the high-temperature
accessory. Coefficients of volume expansion of the low- and high-temperature forms of
Y2O3 were determined from the variation of the lattice parameters with temperature.
* Department of Chemistry, Indian Institute of Technology, Kanpur, India.
t Department of Metallurgical Engineering, Indian Institute of Technology, Kanpur, India.
3586
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MEHROTRA, CHANDRASHEKAR, RAO AND SUBBARAO 3587
The electrical conductivities of the pellets of various oxides were measured with a con-
ductivity cell made of a Kovar tube (2 in. diam., 14 in. long). I n this apparatus, the measure-
ments could be made under vacuum or controlled atmospheres in the temperature range
25-900C. The electrodes were made of Kovar and were insulated from the body of the cell.
The conductivity measurements were made by means of a 1608 General Radio impedance
bridge at a frequency of 1 kc/sec. The temperature of the sample was measured with a
chromel-alumel thermocouple and a Leeds-Northrup millivolt potentiometer. Cylindrical
pellets (1 cm diam., 3 mm thickness) were prepared by the application of -5000 lb. in.-2
pressure. Two thin platinum foils were placed on either side of the pellet prior to the
application of pressure. The conductivity measurements obtained by this procedure were
reproducible and reliable.
The conductivity of La203 and Nd2O3 was measured in dry air as well as in moist air
( p ~ ~ 0 ~ 4 0 mm Hg). The conductivity of Pr2O3 was measured in an atmosphere of pure
and dry hydrogen in order to avoid oxidation. The activation energies Q for the conduction
process for the C form were estimated by plotting log 0 against 1/T. The Q for the high
temperature A forms were obtained by taking the slope of the log 0 against l/Tcurve while
cooling from a high temperature (beyond the transformation temperature) to room tem-
perature.
Reflectance spectra of NdzO3 samples were obtained by employing a Beckman DU
spectrophotometer fitted with the reflectance accessory. U.S.P. magnesium carbonate was
used as the reference as recommended by the U.S. National Bureau of Standards (circ. 484).
- 0%-
x
1 1 1 1 1 1 1 1 1 1 I l l
RESULTS AND DI SCUSSI ON
C - 4 TRANSFORMATION OF La203
The C form of La203 has not been established hitherto, possibly because the
C+A transformation takes place well below the decomposition temperature of
La(OH)3 or other compounds of lanthanum.2 When La(OH)3 was decomposed under
vacuum amorphous La203 was obtained. The amorphous La203 crystallizes to
U
- t 3. n
- - 1 L 04
the C form on slowly heating it to 400C. The lattice parameter of C-La203 was
1 1.39 r f r 0.03 A, in excellent agreement with the value expected from the linear relation-
ship between the unit-cell parameter and the cation radius for C-type rare earth
sesquioxides.2 The DTA curve of the amorphous oxide showed an exothermic peak
at -400C due to crystallization and a broad endothermic peak centered around
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3588 TRANSFORMATIONS OF RARE EARTH SESQUIOXIDES
600C due to the C 4 A transformation. The transformation is apparently sluggish.
The energy of activation of the transformation was estimated to be -20 kcal/mole.
The conductivity data of La203 (fig. 1) shows a break around 590C due to the
C4 A transformation. The transformation temperature is considerably lowered
( N 550C) in the presence of water vapour. For C-La203, the values of the activation
energy, Q, for the conduction process were 1.05 and 049 eV respectively in dry and
moist air. The activation energy for A-La2O3 is N 1.19 eV.
C-.A TRANSFORMATION OF Nd2O3
The reported C+A transformation temperatures of Nd203 33 697 vary widely.
Freshly prepared and dried Nd(OH)3 when subjected to DTA shows an endothermic
peak around 400C due to the decomposition and another peak centred around 550C
due to the C+A transformation. The energy of activation Ea for the transformation,
was estimated to be about 75 kcal/mole.
The electrical conductivity data showed a brezk around 550C due to the C+A
transformation. The transformation temperature seems to be slightly lower in the
presence of moisture (- 520C). The activation energies Q for C-Nd203 in dry and
moist air were 1.26 and 1-23 eV respectively while that for A form was roughly
0.75 eV.
C-Nd203 is light pink in colour and changes to light blue on transformation to the
A form. The reflectance spectrum of the oxide shows shifts of the bands in the visible
region to longer wavelengths.
C+A TRANSFORMATION OF Pr203
The C+A transformation of Pr2O3 has been investigated by Sastry, Mehrotra
and Rao.4 By taking the X-ray patterns of samples heated to different times in the
temperature range 720-850C, the kinetics of the transformation was followed.
The energy of activation of the transformation is estimated to be about 65 kcal/mole
by fitting the data to the first order rate equation.
The conductivity data of Pr2O3 clearly showed a break due to the C+A trans-
formation around 780C. The activation energies Q for the conduction process
were 0.84 and 0.86 eV for the C and A forms respectively.
PHASE TRANSFORMATION OF c-Y203
Yttrium sesquioxide has been reported to exist only in the C form.2 The quenched
samples of Y203 produced by sprinkling a fine powder through an argon plasma jet
are also found in the C form.1 When the DTA curves of yttrium oxalate and carbon-
ate were recorded up to 1 lOO"C, a small endothermic peak was noticed around 1000C.
On cooling, a corresponding small exothermic peak was also noticed around this
temperature. The X-ray diffraction traces of Y2O3 recorded in the range 25-1100C
(fig. 2) showed the appearance of a new reflection at as low a temperature as 390C
which increased in intensity as the temperature was further increased. The pattern
recorded at about 900C corresponded to a new form of Y2O3. This new form
has been tentatively assigned to a hexagonal structure with a = 9.80 A and c = 10.17A
at 900C. The assignment is, however, not definitive and a monoclinic structure
for the high temperature phase could not be excluded.
The X-ray diffraction traces in fig. 2 show the coexistence of the low-temperature
and the high-temperature forms of Y2O3 over a wide range of temperatures. The
X-ray pattern of a sample quenched from 1OOO"Cgradually to room temperature
showed that a small proportion of the high temperature form can get frozen in the
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MEHROTRA, CHANDRASHEKAR, RAO AND SUBBARAO
3589
C form. Fast quenching, however, results in the complete transformation back to
the C form. The coexistence of the two phases over a wide range of temperatures
is typical of a higher order or continuous transformation 8 and explains the observation
of the small transformation peak in the DTA curve. The energy of activation for
FIG. 2.-X-ray pattern of Y2O3 as a function of temperature. The value
of 28 of the peak due to the C-form at 25C is 28.95" . The 28 value of
the high-temperature form is 28" at 916C.
30 29 26
28
the transformation of Y2O3 has been estimated to be low (maximum value of Eaw 10
kcal/mole).
The coefficients of volume expansion for the low-temperature C form was
2.64 x 10-3 cm3/mole deg., while it was 2-33 x 10-2 cm3/mole deg. for the high-tem-
perature form. The higher value of the coefficient for the high-temperature form
seems to be consistent with the close-packed structure of this phase.
CONCLUSIONS
The C+A transformations of La2O3, Nd2O3 and Pr& are irreversible and seem
to follow the first-order rate law. The energies of activation for the transformation
of Pr203 and Nd203 are appreciably higher compared to that of La2O3. The Ea
value as well as the transformation temperature reported for Nd2O3 by Stecura7
are much higher than those reported here. It is possible that samples examined by
other workers had appreciable impurities in them. Any other heavier rare earth
impurity increases the stability limit of the C form. The Ea values for the C to B
transformations of Sm2O3, Eu2O3 and Gd2O3 vary in the range 150-190 kcal/mole.7
The transformation temperatures as well as the Ea values increase with the decreasing
size of the rare earth ion. The transformations of the rare earth sesquioxides are
associated with a reconstructive mechanism, involving changes in the primary co-
ordination.9 The increase in the transformation temperature as well as the EG value
with the increasing size of the cation suggests that the reaction rates are controlled
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3590 TRANSFORMATIONS OF RARE EARTH SESQUIOXIDES
by the diffusion or rearrangement of the larger oxygen ions rather than that of the
smaller cations.
The electrical conductivity data on the phase transformations of the oxides show
that moisture decreases the transformation temperature as had been suspected
earlier.4, 10 This may be due to the higher mobility of the ions and the vacancies in
the presence of water vapour. One possibility is that moisture produces hydroxyl
ions which by virtue of their lower charge will have higher mobility than the oxide
ions. There appears to be no simple relation between the Q values for the high
temperature close-packed structure ( A form) and the low temperature defect structure
(C form). Measurement of the transference numbers for the ions and electrons will
contribute to an understanding of the conduction mechanism in these oxides.
The phase transformation of Y203 which is an important solid state material had
not been observed, possibly because the transformation is reversible and occurs over
a wide range of temperatures. The DTA peaks are not clearly seen in many such
continuous transformations.11
The authors thanks are due to the National Bureau of Standards, U.S.A. for the
award of a research grant (G-5 1) through their Special International Programme.
Thanks are also due to Dr. T. Y. Tien of the Westinghouse Research Laboratories,
Pittsburgh, U.S.A., for supplying the high temperature X-ray data on Y203.
1 Eying and Holmberg, in Nonstoichiometric Compounds, (Adv. Chem. Series), 1963, 39, 46.
2 Roth and Schneider, J. Res. Nut. Bur. Stand., A 1960, 64, 309.
3 Warshaw and Roy, J. Physic. Chem., 1961, 65, 2048.
4 Sastry, Mehrotra and Rao, Trans. Faruday Soc., 1966,62, 1632.
5 Borchardt and Daniels, J. Amer. Chem. SOC., 1957, 79, 41.
6 Blum and Maguire, Amer. Cerum. SOC. Bull., 1960, 39, 310.
7 Stecura, US . Bur. Mines Report 6616 (1965).
8 Ubbelohde, Quart. Rev. 1957, 11,246.
9 Buerger in Phase Transformations in Solids, ed. Smoluchowski, (John Wiley, New York, 1951).
10 Chapin, Finn and Honig, 4th Rare Earth Conference (1964).
11 Rao and Rao, J. Materials Sci., 1966, 1, 238.
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