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AbstractSolid solutions Ni0.5xCdxZn0.5Fe2O4 (x = 0, 0.15, 0.30) were prepared by solid-state synthesis and
characterized by FTIR spectroscopy. The FTIR spectra of synthesized ferrites showed two absorption bands
(1 and 2) in the range 400600 cm1 belonging to tetrahedral (A) and octahedral (B) interstitial sites in the
spinel lattice. The force constants for tetrahedral (Kt) and octahedral sites (Ko) were determined, as well as
Youngs modulus (E), rigidity modulus (G), bulk modulus (B), Debye temperature (D), and velocity of
transverse (Vt) and longitudinal (Vl) elastic waves. The relevant interionic cationanion, cationcation dis-
tances and bond angles are also reported.
Keywords: solid-state synthesis, synthesis by firing, NiZn ferrites, FTIR spectra, elastic modulus, force con-
stants
DOI: 10.3103/S1061386217010083
33
34 PATIL et al.
Force constants
Distribution Complete
of cations ness of
among non reaction of
equivalent Analysis of formation
sites IR spectra
Nature of
metal Elastic
oxygen constants
bonds
complexes in spinel structure [13, 14]. The IR spectra As is known, an increase in site radius reduces the
of Cd-substituted nickel ferrites were found [13] to fundamental frequency and therefore the center fre-
exhibit two bands in the range 400700 cm1 but no quency should shift toward lower values. The increase
absorption bands above 700 cm1. in site radius may be expected to be due to replacement
of smaller Ni2+ ions (0.069 nm) by larger Cd+2 (0.097
According to Waldrons classification [4], the unit nm) ions. This is due to the fact that substituted Cd2+
cell of cubic spinel can be formed by tetrahedral (A) ions preferentially occupy the A site only and the dif-
and octahedral (B) sites. Accordingly, band 1 can be ference between the ionic radii of A-site Fe3+ (0.064
assigned to stretching vibrations of the tetrahedral nm) and Cd2+ (0.097 nm) cations is much larger as
metaloxygen (MeO) bond while band 2, to the compared to those of B-site Fe3+ (0.064 nm) and Ni2+
metaloxygen vibrations in octahedral sites. The val- (0.069 nm) cations [14].
ues of 1 are higher than those of 2, thus indicating
that the normal vibration mode of the tetrahedral Our FTIR spectra show some splitting in the
complexes is higher than that of the corresponding absorption band caused by the presence of small
octahedral sites. This may be due to a shorter bond amounts of Fe2+ ions in the ferrite. The absorption
length in the tetrahedral site compared to that in the band edges, as well as tetrahedral (Kt) and octahedral
octahedral one. sites (K0) force constants are given in Table 1.
According to Waldron [4], the force constants are
calculated using the following expressions:
K0 = 0.942128M1 22 /[MA + 32], (MA is molecular
x v1 v2 weight on A-site)
0 597 418
0.15 578 416 Kt = 0.04416MB12 [V/V + 3], (MB is molecular
0.30 570 420 weight on B-site)
T, rel. units
Table 1. Position of FTIR band edges and force constants for Ni0.5xCdxZn0.5Fe2O4 ferrites; cation distribution formula:
[Zn0.5CdxFe0.5x]A[Ni0.5xFe1.5+x]BO4
ions (MeMe) (b, c, d, e, and f) and between the cat- fore, the interaction between the moments on the A
ion and anion (MeO) (p, q, r, and s) were calculated and B sites is strongest. The BB interaction is much
using the measured values of lattice constant (shown in weaker and the most unfavorable situation occurs in
Fig. 3). For AA and BB, the angles are too small or the the AA interaction.
distances between the metal ions (Me) and the oxygen The ferrimagnetism of ferrites is explained on the
ions (O) are too large. The best combinations of dis- basis of AB interaction. An individual A site interacts
tances and angles are found in the AB interactions. with a single B site, but each A site is linked to four
For an undistorted spinel, the AOB angles are such units and each B site is linked to six such units
about 125 and 154. The BOB angles are 90 and [15]. Thus he overall strength of the magnetic interac-
125 but in the latter, one of the BO distances is large tions (AB, BB, and AA) depends upon the bond
[15]. In the AA case, the angle is about 80. There- length and bond angles between the cations and cation
A A
B B q
P C P P
A
P
b P r r
q e d
B B
r s
B A
B
p = a(0.5 u) b = ( a / 4) 2
c = ( a / 8) 11
q = a ( u 0.125) 3
d = ( a / 4) 3
r = a ( u 0.125) 11
e = (3 a / 8) 3
s = a ( u + 0.5) 3 f = ( a / 4) 6
3
Fig. 3. Interionic distances between Me cations (b, c, d, e, and f), between Me cation and anion (p, q, r, and s), and bond angles .
anion. The strength of interaction is directly propor- The bond angles (1, 2, 3, 4 and 5) were calcu-
tional to bond angle but inversely proportional to bond lated (see Table 2) by using basic trigonometric princi-
length. ples and the following formulae:
1 p + q c 1 p + r 2 e2
2 2 2 2
1 = cos , 2 = cos ,
2 pq 2 pr
2p b
2 2
1 p + s f
2 2 2
3 = cos 1 2 , 4 = cos ,
2p 2 ps
1 r + q d
2 2 2
5 = cos .
2rq
The interatomic distances tetrahedral bond The results are presented in Fig. 4.
length (dAx), octahedral bond length (dBx), shared
tetragonal edge (dAEx), shared octahedral edge (dBxE)
and unshared octahedral edge (dBxEu) have been cal- 3.2. Elastic Properties
culated according to [16, 17]:
Elastic properties of ferrites are of key importance
Table 3. Stiffness constants (C11, B), longitudinal elastic wave (Vl), transverse elastic wave (Vt), mean elastic velocity (Vav),
rigidity modulus (G), Poissons ratio (P), Youngs modulus (E), and Debye temperature ()
x C11, GPa B, GPa Vl, m/s Vt, m/s Vav, m/s G, GPa P E, GPa , K
0.0 160.94 160.94 5480.92 2816.44 2883.63 53.648 0.35 72.425 346.15
0.15 166.04 166.04 5570.25 2862.30 2884.74 55.346 0.35 74.717 344.63
0.30 175.67 175.67 5731.71 2945.18 2885.40 58.557 0.35 79.053 344.34
vibration [18, 19]. Debye temperature simplifies the and Debye temperature der5ived from IR data well
integration of the heat capacity. For isotropic mate- agree with those reported for other ferrite systems [14,
rial, the values of stiffness constants (C11 = C12), veloc- 1822]. Elastic moduli and Debye temperature can be
ity of longitudinal (Vl) and transverse elastic wave (Vt), determined through IR spectral analysis and also from
mean elastic velocity (Vav), rigidity modulus (G), Pois- increase in elastic constants with increasing x [18, 19].
sons ratio (P) and Youngs modulus (E) were calcu- It should be noted that the values of elastic moduli and
lated as shown below and collected in Table 3. Debye temperature determined through ultrasonic
pulse transmission technique for NiCd ferrite system
1/2
, V t = (V l 3) ,
synthesized by conventional double sintering ceramic
C11 = C12 = K av a , V l = 11
C
dx technique showed a decrease with increasing cad-
1/3 mium content.
V M = V i 3V t 3 V t 3 + 2V i 3 , G = d xV t2,
6500
4
dAx dBx dAxE dBxE dBxEu
Bond/edge lenght,
5500
3
V, m/s
4500 V1
2 Vt
Vav
3500
1
2500
0 0.1 0.2 0.3
0 0.1 0.2 0.3 x
x
Fig. 5. Variation in velocities of longitudinal (Vl) and trans-
Fig. 4. Bond and edge lengths vs. cadmium content x. verse (Vt) elastic waves vs. cadmium content x.
3.80
LA LB
L,
3.30
2.80
0 0.1 0.2 0.3
x
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