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Archives of Physics Research, 2011, 2 (4):104-107
(http://scholarsresearchlibrary.com/archive.html)
ISSN : 0976-0970
CODEN (USA): APRRC7
Crystalline structural changes in Na-doped Y-Ca-Cu-O oxides

D. S. Choudhary
Dhote Bandhu Science College, Gondia, Maharashtra, India
______________________________________________________________________________
ABSTRACT
Na-doped YCa2Cu4O7- oxides are prepared by solid state diffusion of heating the reacting oxides
(standard ceramic technique). The X-ray diffraction measurements show that the Na-doped
YCa2Cu4O7- is single phase orthorhombic structure by annealing below 900C under oxygen
atmosphere. It is observed that, increase in Na content, the orthorhombic distortion decreases.
Keywords: Oxide superconductor, orthorhombic structure, tetragonal symmetry.
______________________________________________________________________________
INTRODUCTION
Ever since the discovery of high temperature superconductivity in the Y-Ba-Cu-O system [1]
several isovalent and aliovalent substitutions for Y and Ba were made by different groups in
order to investigate the structureproperty relationships in these compound. Investigation on cosubstitution of Ca2+ for Y3+ and La3+ for Ba2+ in Y-Ba-Cu-O system, a new tetragonal
CaBaLaCu3O7- was discovered independently by two groups [2, 3]. After extensive survey on
cuprate oxide superconductors, we though that the field is interesting with replacement of Ba
by Ca and partial substitution of Na for Y in the oxide having general chemical
composition Y1-xNa xCa 2Cu 3O 7- for x = 0.0, 0.1, 0.2, 0.3 & 0.4. The purpose of present work
is to study the effect of change of concentration of Na for Y in Y1-xNaxCa 2Cu 3O 7- and to
characterize these for structural point of view. The oxides with general chemical formula Y1-xNa
xCa2Cu3O7- for x = 0.0, 0.1, 0.2, 0.3, & 0.4 are prepared by oxide method. Each sample is
prepared with same atmosphere and the identical preparational procedure is adopted for the all
samples studied here. Phase purity is checked by X-ray diffraction analysis. X-ray diffractometry
is used for identification of these samples using same X-radiation.
MATERIALS AND METHODS
The simplest method of preparing oxide superconductor in a sintered polycrystalline state is a
solid state diffusion of heating the reacting oxides (standard ceramic technique), which are easily
decomposed to oxides. In this method, the impurity addition is avoided. The formation of
compounds depends on many factors such as particle, size of reactants, sintering temperature and
104
D. S. Choudhary
Arch. Phy. Res., 2011, 2 (4):104-107
______________________________________________________________________________
atmosphere etc. This method for preparation of oxide compounds is extensively used due to its
simplicity [4].
All the compounds having the chemical composition Y1-xMxCa2Cu3O7- (where M = Na for x =
0.0, 0.1, 0.2, 0.3, and 0.4) are prepared by using high purity annular grade oxide under identical
condition. The reacting oxides Y2O3, Na2O3, CaCO3 and CuO (All 99.9 % pure) first heated
individually in air at 200C for 5 - 6 hours to remove the moisture. They are intimately mixed
together in the proper molar ratio. To achieve homogeneity and for uniform grain size in
polycrystalline form, the mixtures are continuously ground about 5 - 6 hours under A. R. grade
acetone in a agate mortar. After grinding the mixture, they are dried in air and heated in air at
800 C for 24 hours in an electrical furnace. The resulting specimen following the reaction were
ground and retreated at 900 C for 24 hours to obtain a homogenous single phase sample. The
resultant black product was reground and cold pressed into pellets, which are sintered in air at
900 C and 950 C for 24 hours. These pellets were annealed under oxygen flow at 450 C for 12
hours followed by slow cooling at the rate of 1 C/min until room temperature is reached.
For the pelletalization, the resulting mixture obtained was added with 5 % polyvinyl acetate
(PVA) solution in AR grade acetone as a binder and mixed thoroughly. This PVA mixed sample
is then pressed in hydraulic press for about 5 minutes. The pellets thus obtained are heated in an
electric furnace at about 300 C for about 4 hours to remove the binder and then PVA removed
pellets are fired at higher desired temperature to obtain the resulting oxides. These pellets thus
obtained are crack free and hard. One pellet of each sample was then finely powered in an agate
mortar for characterization. Philips W-1710 X-ray diffractometer and using Cu-K radiation in the
2 range of 0-60 is carried the XRD.
RESULTS AND DISCUSSION
The XRD pattern are taken on sintered 1-xNaxCa2Cu3O7- sample for x = 0.0, 0.1, 0.2, 0.3 and
0.40. As all the oxides have same chemical formula with changes in cations which are not
differing heavily in ionic sizes, all of them are expected to have a similar crystal structure. With
this idea in mind, all the peaks in the XRD pattern of samples have been indexed for
orthorhombic structure. The observed d values found to be in good agreement with the
calculated values. The lattice parameters, unit cell volume and orthorhombic distortion which is
defined as (b-a) corresponding to the concentration of rare earth Na substituted for is shown
in Table 1.
Table 1: Structural parameters
Composition
(x)
0.0
0.1
0.2
0.3
0.4
Unit cell parameters

a
(A)
3.643
3.678
3.689
3.702
3.707
b (A)
3.838
3.803
3.797
3.764
3.765
c (A)
11.795
11.755
11.71
11.680
11.676
Unit cell
Volume
(A)3
164.915
164.442
164.023
162.75
162.96
Orthorhombic
distortion
(b-a) (A)
0.195
0.125
0.108
0.062
0.058
The variation of lattice parameters a, b and c with sodium content x is shown in Figure 1,
Figure 2 and Figure 3 respectively.
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D. S. Choudhary
Arch. Phy. Res., 2011, 2 (4):104-107
______________________________________________________________________________
The lattice parameter a increases with the Na content x while b decreases with increase in
content x up to x = 0.3 but increases for x = 0.4. Further, the lattice parameter c decrease
with the Na content x 0.4. This is due to the geometrical considerations. All the compounds
maintain a orthorhombic perovskite Structure. c parameter and unit cell volume decrease
drastically with increasing sodium concentration x up to 0.2. It may be due to introduction of
Na+ which has the comparable ionic radius as that of Y3+. But remains nearly constant for system
with x 0.3. On the other hand, electrons will be introduced into antibonding Cu-O orbitals on
the a-b plane by the substitution which tends to expand the a-dimension [5]. This was attributed
to comparable size of Na+ and y3+ which has pronounced effect on c parameter because the
lattice parameter c is approximately three times a and b. It appears that among the system
studied, it attains maximum contraction at sodium content x 0.3. A similar observations was
made by Ono et al [6] where c and a decreases drastically for the concentration of Sr2+ 0.5
on Ba side and nearly constant for system with x > 0.5. Similar results have been reported for
La4-xCaxBa3Cu7O2 [7], La3Ba4-xCaxCu7O2 [8], La3-xCa2xBa3xCu6O2 [9] , Ba2-xKxCu3O7- [10]
and (Y1-xSrx)(Ba1.5Sr0.5)Cu3O7- [11].
The variation orthorhombic distortion (b-a) with Na content x is shown in Figure IV. All the
oxides crystallize in orthorhombic symmetry but the extent of orthorhombic distortion decrease
with x. It is seen that the lattice parameter a increases with increase in x and may approach
b at higher values of x and may result the phase transition from orthorhombic to tetragonal
symmetry.
The similar is reported in Raman et al [10] for Ba2-xKxCu3O7- . The decrease in (b-a) is may be
due to decrease in oxygen content as a consequence of increase in Na concentration.
106
D. S. Choudhary
Arch. Phy. Res., 2011, 2 (4):104-107
______________________________________________________________________________
CONCLUSION
The YCa2Cu4O7- compounds can be prepared at an ordinary pressure of oxygen. The
compounds crystallize to orthorhombic system with single phase. The lattice parameter c is
roughly three times the parameter a and b.
REFERENCES
[1] M. K. Wu, J. R. Ashburn, C. J. Tomk, P. H. Hor, R. L. Meng, L. Gao, Z. J. Fluang, Y. Q.
Wang and C. W. Chu, Phys. Rev. Lett., 1987, 58, 908.
[2] Y. Tokura, J. B. Torrance, T. C. Haung and A. I. Nazzal, Phys. Rev. B, 1988, 38, 7156.
[3] A. H. Carim, F. De Jony and D.M. De Leeuw, Phys. Rev. B, 1998, 38, 7009.
[4] E. M. Engler, CHEMTECH, 1987, 17, 542.
[5] A. T. Matveev, E. Takayama, Muromachi, Physica C, 1995, 254, 26.
[6] A. Ono, T. Tanaka, H. Noraki and Y. Tshizawa, Jpn. J. Appl. Phys., 1987, 26, 1687.
[7] D. S. Wu, H. C. I. Kao, M. K. Wu and C. M. Wang, Physica C., 1993a, 214, 261.
[8] D. S. Wu, Y. F. Wang, H. C. I. Kao and C. M. Wang, Physica C., 1993b, 212, 32.
[9] Y. D. Leu, W. N. Huabg, C. M. Wang and H. C. I. Kao, Physica C., 1996, 261, 284.
[10] N. S. Raman and B. Viswanathan, Bull. Mater. Sci., 1993, 16, 381.
[11] F. C. Matacotta, T. Moyo, J. Ramosarhuis, C. U. Segre, S. A. Siddiqui and A. Migliori, Bull.
Mater. Sci., 1991, 14, 279.
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Crystalline structural changes in Na-doped Y-Ca-Cu-O oxides

Unit cell parameters

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