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ISSN 1061-3862, International Journal of Self-Propagating High-Temperature Synthesis, 2017, Vol. 26, No. 1, pp. 33–39.

© Allerton Press, Inc., 2017.

FTIR Spectra and Elastic Properties
of Cd-Substituted Ni–Zn Ferrites1
M. R. Patila, M. K. Rendaleb, S. N. Mathadc,*, and R. B. Pujara,d
a
S.S. Arts College and T.P. Science Institute, Sankeshwar, India
bDepartment of Engineering Physics, K.L.S. Gogte Institute of Technology, Belagavi, India
c
Department of Engineering Physics, K.L.E. Institute of Technology, Hubli, India
d
Department of Physics, P.C. Jabin Science College, Hubli, India
*e-mail: physicssiddu@gmail.com
Received August 2, 2016

Abstract⎯Solid solutions Ni0.5–xCdxZn0.5Fe2O4 (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
(ν1 and ν2) in the range 400–600 cm–1 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
Young’s modulus (E), rigidity modulus (G), bulk modulus (B), Debye temperature (ΘD), and velocity of
transverse (Vt) and longitudinal (Vl) elastic waves. The relevant interionic cation–anion, cation–cation dis-
tances and bond angles are also reported.

Keywords: solid-state synthesis, synthesis by firing, Ni–Zn ferrites, FTIR spectra, elastic modulus, force con-
stants
DOI: 10.3103/S1061386217010083

1. INTRODUCTION In this communication, we report on detailed
FTIR analysis of the Ni0.5–xCdxZn0.5Fe2O4 (x = 0,
Ferrites deserve attention due to their broad practi- 0.15, 0.30) ferrites prepared by solid-state synthesis.
cal application. Ferrite nano particles are the most
explored magnetic nano particles up to date. Ferrites
are widely used in high-frequency applications, 2. EXPERIMENTAL
because an AC field does not induce undesirable eddy High purity nickel oxide, cadmium oxide, zinc
currents in insulating material [1–3]. The electrical, oxide, and iron oxide were weighed accurately in
magnetic, and dielectric properties of ferrite materials required molar proportions and mixed mechanically
depend on their chemical composition, cation distri- in an agate mortar in acetone medium. The low-cost
bution, and synthesis procedure. The vibrational, solid-state synthesis procedure was essentially the
electronic, and magnetic dipole spectra can give infor- same as reported elsewhere [13]. IR spectra of thick
mation about the position and valence of the ions in films were recorded in the range 400–750 cm–1 with a
the crystal lattice. The FTIR technique shows marked Perkin Elmer (Spectrum-2000) FTIR spectropho-
selectivity to chemical composition. Various bands tometer.
present in IR spectra of ferrites can be regarded as fin-
ger prints of characteristic functional groups and 3. RESULTS AND DISCUSSIONS
bonds [4–7]. The information that can be grabbed 3.1. Structural and Vibrational Analysis
from analysis of FTIR spectra is schematically illus-
trated in Fig. 1. To date, several nanosized ferrites have The IR absorption spectra recorded in the range
been fabricated by using solid-state reactions, co-pre- 750–400 cm−1 are given in Fig. 2. It is a well-known
cipitation technique, sol–gel combustion, modified that normal and inverse cubic spinels have four funda-
oxidation process, forced hydrolysis, hydrothermal mental IR bands. Two of them, around 600 and
process, ball-milling, aerosol method, and sucrose 400 cm−1, are common for almost all spinel-type fer-
precursor technique [7–13]. rites. In the present work, bands ν1 and ν2 were found
within the ranges 570–597 and 418–420 cm−1, respec-
1 The article is published in the original.
tively, and attributed to tetrahedral and octahedral site

33

097 According to Waldron’s classification [4]. 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.04416MBν12 [V/V + 3]. This may be due to a shorter bond amounts of Fe2+ ions in the ferrite.30 570 420 weight on B-site) T. 26 No.30 Interaction between magnetic moments (μB) on lattice sites with regard to the strength of interactions between moments on various sites. 1 2017 .15 action or exchange force between the moments of two metal ions on different sites depend on distance between these ions and the oxygen ion that links them X=0 and also on the angle between the three ions [15]. complexes in spinel structure [13. The increase absorption bands above 700 cm–1. units U = 2K0/(MBν12 – 2K0). in site radius may be expected to be due to replacement of smaller Ni2+ ions (0. Information that can be grabbed from analysis of FTIR spectra. rel. 2. 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 400–700 cm–1 but no quency should shift toward lower values.34 PATIL et al. the force constants are calculated using the following expressions: K0 = 0. Interionic distances between the cat- INTERNATIONAL JOURNAL OF SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS Vol. 14]. to the compared to those of B-site Fe3+ (0. as well as tetrahedral (Kt) and octahedral octahedral one. sites (K0) force constants are given in Table 1. the unit nm) ions. 3.5–xCdxZn0. 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. 1.15 578 416 Kt = 0. FTIR spectra of Ni0. The IR spectra As is known. (MA is molecular x v1 v2 weight on A-site) 0 597 418 0.097 nm) cations is much larger as metal–oxygen (Me–O) bond while band ν2. Accordingly. ues of ν1 are higher than those of ν2. According to Waldron [4]. The interaction is strongest at an angle of 180° and also 750 700 650 600 550 50 450 400 where the interatomic distances are shortest. The absorption length in the tetrahedral site compared to that in the band edges. (0.5Fe2O4. (MB is molecular 0. shown in Fig.942128M1ν 22 /[MA + 32]. V = (64 – 2MAU)/MB X = 0.069 nm) cations [14].069 nm) by larger Cd+2 (0. The con- v. band ν1 can be ference between the ionic radii of A-site Fe3+ (0. 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 Fig. The val.064 nm) and Ni2+ metal–oxygen vibrations in octahedral sites. the negative inter- X = 0. cm–1 figuration of ion pairs in spinel ferrites with favorable distances and angles for magnetic interactions are Fig.064 assigned to stretching vibrations of the tetrahedral nm) and Cd2+ (0.

and f). cm–1 Force constants. There. 26 No. 1 2017 .11 597 418 164. M Position of band edge.5 – u) b = ( a / 4) 2 c = ( a / 8) 11 q = a ( u – 0. the angle is about 80°.125) 3 d = ( a / 4) 3 r = a ( u – 0. and s) were calculated and B sites is strongest. c. e.95 134.62 ions (Me–Me) (b.62 113. the A–O–B angles are such units and each B site is linked to six such units about 125 and 154°. length and bond angles between the cations and cation – A A B B q P C P P φ φ A φ φ P b P r φ r q e d B B r s B A B φ = 126° φ = 154° φ = 90° φ = 125° φ = 79° p = a(0. e.69 578 416 175. d. and f) and between the cat. fore.11 112. r.5) 3 f = ( a / 4) 6 3 Fig.63 104.79 0. q. An individual A site interacts tances and angles are found in the A–B interactions. INTERNATIONAL JOURNAL OF SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS Vol.5–x]A[Ni0. distances between the metal ions (Me) and the oxygen The ferrimagnetism of ferrites is explained on the ions (O) are too large. weight.59 112. Interionic distances between Me cations (b.26 570 420 192.5CdxFe0. between Me cation and О anion (p. one of the B–O distances is large tions (A−B. with a single B site. d. For A–A and B–B.5–xCdxZn0.5–xFe1.15 148. 3). The B–B interaction is much using the measured values of lattice constant (shown in weaker and the most unfavorable situation occurs in Fig. cation distribution formula: [Zn0. B−B. FTIR SPECTRA AND ELASTIC PROPERTIES 35 Table 1.09 105.55 139.5Fe2O4 ferrites.15 69. the angles are too small or the the A–A interaction.0 60. Thus he overall strength of the magnetic interac- 125° but in the latter. the interaction between the moments on the A ion and anion (Me–O) (p. N/m x Site A Site B ν1 ν2 Kt K0 Kav (M1) (M2) 0. The B–O–B angles are 90° and [15]. and s).5+x]BO4 Mol. q. The best combinations of dis. but each A site is linked to four For an undistorted spinel. In the A–A case.30 77. and A−A) depends upon the bond [15]. r.125) 11 e = (3 a / 8) 3 s = a ( u + 0. Position of FTIR band edges and force constants for Ni0. basis of A–B interaction. 3.92 103. and bond angles φ. c.73 0.

17]: Elastic properties of ferrites are of key importance ( ) for industrial applications because they define the 12 d Ax = a(u − 1 4) 3.4949 f 5.e. e. ⎝ 2p ⎠ ⎝ 2 ps ⎠ −1 ⎛ r + q − d ⎞ 2 2 2 θ 5 = cos ⎜ ⎟. The strength of interaction is directly propor.8 133.7170 3. 1 2017 .3 67. 4 64 Elastic properties of ferrites can be characterized by 1 d AxE = a(2u − ) 2. 26 No.4395 5. ⎝ 2rq ⎠ The interatomic distances – tetrahedral bond The results are presented in Fig.30 Lattice constant a. s) and bond angles (θ) x = 0.0514 Me–O distance.8040 2.5073 Me–Me distance. Å 8. shared tetragonal edge (dAEx).0308 2. Å d 3.5 Bond angles θ θ2 133.0407 2.92 126.9777 1. f and p.56 97.4720 3. θ3.5 120. r. d BxE = a(1 − 2u) 2.4157 8.7050 0. d.92 θ5 67.7904 2.1284 5.56 97.9076 3.4890 3.3747 8.9935 anion.6633 e 5.8 θ3 97.9270 1.7068 Edge and bond lengths dAxE 3.9754 2.5 120.7365 θ1 120. FTIR spectroscopy as suggested in [18. ples and the following formulae: −1 ⎛ p + q − c ⎞ −1 ⎛ p + r 2 − e2 ⎞ 2 2 2 2 θ1 = cos ⎜ ⎟ .0 x = 0. 20].8886 3. d Bx = a 3u − 11 u + 43 .9282 s 3.9371 dBx 0.9609 2.1315 3.15 x = 0. θ 4 = cos ⎜ ⎟. The bond angles (θ1.4600 b 2.8188 dBxEu 2. θ 2 = cos ⎜ ⎟. the highest tem- perature that can be achieved due to a single normal INTERNATIONAL JOURNAL OF SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS Vol.9681 1. Å r 3. θ2..7033 0. 3.6989 3.6264 3. octahedral bond length (dBx).2. Elastic Properties culated according to [16.56 θ4 126. d BxEu = a 4u − 3u + 11 .3 67.6441 3.9634 2.4662 5.1633 dBxE 2. c. Interionic distances (b.3 dAx 1.9176 1. i. ⎝ 2 pq ⎠ ⎝ 2 pr ⎠ ⎛2p − b ⎞ 2 2 −1 ⎛ p + s − f ⎞ 2 2 2 θ3 = cos −1 ⎜ 2 ⎟ . Table 2. The 2 Debye temperature (ΘD) is the temperature of crys- 2 ( d BxE = a(1 − 2u) 2. 4. 2 strength of the materials in different strain conditions.9911 c 3.8 133.92 126. q.1807 p 1.9881 q 2. θ4 and θ5) were calcu- tional to bond angle but inversely proportional to bond lated (see Table 2) by using basic trigonometric princi- length.9779 2.36 PATIL et al.1535 5. 16 ) tal’s highest normal vibration. length (dAx).1468 3. shared octahedral edge (dBxE) and unshared octahedral edge (dBxEu) – have been cal.

mean elastic velocity (Vav).053 344. m/s 4500 V1 2 Vt Vav 3500 1 2500 0 0.94 5480. The elastic parameters 6500 4 dAx dBx dAxE dBxE dBxEu Bond/edge lenght. cadmium content x. Å 5500 3 V. and G with increasing x (Table 3) can be interpreted in terms of due to embedding larger magnetic Cd2+ ions into the B interatomic bonding [21]. hopping lengths LA and LB tend E = 2G (1 + P ). Bond and edge lengths vs. V l = ⎜⎛ 11 ⎟⎞ C ⎝ dx ⎠ technique showed a decrease with increasing cad- 1/3 mium content. LB = a 2 . 26 No.92 2816. and sublattices and migration of nonmagnetic Ni2+ ions into Vav with increasing cadmium content x is plotted in the A sublattices.15 0. The variation in Vl.30 2884. FTIR SPECTRA AND ELASTIC PROPERTIES 37 Table 3. 19]. GPa B.15 166. agree with those reported for other ferrite systems [14. It should be noted that the values of elastic moduli and lated as shown below and collected in Table 3.25 2862.425 346. The magnitudes of LA = a 3 . rigidity modulus (G). determined through IR spectral analysis and also from mean elastic velocity (Vav). increase in elastic constants with increasing x [18. Poisson’s ratio (P). GPa Θ. E. rigidity modulus (G).34 vibration [18.04 166. V t = (V l 3) .67 175. 4.3 x x Fig. where a stands for the lattice constant. veloc. and Debye temperature (Θ) x C11. cadmium content x. 1 2017 .35) for all samples.648 0.63 53. Vt. which is consistent with the the. 18–22].1 0. Variation in velocities of longitudinal (Vl) and trans- Fig.94 160.35 79. son’s ratio (P) and Young’s modulus (E) were calcu.557 0. synthesized by conventional double sintering ceramic C11 = C12 = K av a . The distance between magnetic ions (hopping An increase in elastic moduli indicates the length) in tetrahedral A site and octahedral B site were strengthening of interatomic bonding between various calculated by using the following relations [23]: atoms caused by replacement of nickel by cadmium ions as supported by earlier results on variation of elas- tic moduli with Cd content [14]. m/s Vav. 19]. Debye temperature simplifies the and Debye temperature der5ived from IR data well integration of the heat capacity.0 160. approach each other and thus to increase the hopping length.1 0.04 5570. m/s G. 5.74 55. GPa P E. Stiffness constants (C11. Pois. 3.40 58.35 74. transverse elastic wave (Vt). longitudinal elastic wave (Vl). G = d xV t2. GPa Vl. 6. Θ D = . verse (Vt) elastic waves vs. which makes the magnetic ions to Fig.18 2885.3 0 0. P = ⎡3B − 2G ⎤ .30 175. Hopping Length 3 ⎢⎣6B + 2G ⎥⎦ hc V av As is seen in Fig. V M = ⎡⎣V i 3V t 3 V t 3 + 2V i 3 ⎤⎦ . m/s Vt. INTERNATIONAL JOURNAL OF SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS Vol. B = 1 (C11 + 2C12 ). 2πk to grow with increasing x. the values of stiffness constants (C11 = C12). K 0. B).2 0.63 0.71 2945. 5.717 344. rial.35 72.3.67 5731.2 0. Young’s modulus (E). ory of isotropic elasticity [19]. Debye temperature determined through ultrasonic pulse transmission technique for Ni–Cd ferrite system 1/2 . Poisson’s ratio (P) were found to be constant (P = 4 4 0. This can be related to expan- sion of the unit cell caused by an increase in site radius A decrease in the values of B. Elastic moduli and Debye temperature can be ity of longitudinal (Vl) and transverse elastic wave (Vt).346 0. For isotropic mate.44 2883.

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