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CoFe2O4 and ZnxCo1-xFe2O4 are inverse and mixed ferrite respectively.

The magnetic
moments and lattice parameters of these spinel ferrite are given below:

CoFe2O4

CoFe2O4 can be written as (Fe3+)A [Co2+Fe3+]BO4

(5 x1) (3x1) + (5x1)

=5 B =8 B

Net Magnetic moment in Bohr magnetron nB = MB – MA= 8 B -5 B =3B

The relation between nB and magnetic saturation can be written as

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟𝑤𝑒𝑖𝑔ℎ𝑡𝑥𝑀𝑠
nB =
𝑁𝑥𝐵

234.623 𝑥𝑀𝑠
3=
6.023 𝑥1023 𝑥0.927𝑥10−20

Ms = 70.78 emu/gm

Lattice parameter :

The ionic radius of A and B sites for CoFe2O4 can be written as

𝑟𝐴 = 𝐶𝐴𝐹𝑒 r(Fe3+) = 0.645 Å

1 1
𝑟𝐵 = 2 [CBFe r (Fe3+)+CBCo r (Co2+)] =2 [ 0.745+0.645]= 0.695 Å

The lattice parameter, a can be defined as follows


8
ath =3√3 [(𝑟𝐴 + 𝑅𝑜 ) +√3(𝑟𝐵 + 𝑅𝑜 )] ; 𝑅𝑜 = 𝑟𝑎𝑑𝑖𝑢𝑠 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 = 1.32 Å

8
=3√3 [(0.645+1.32)+ √3 (0.695+1.32)]= 8.3986 Å

The substitution of Co with Zn causes variation in magnetization and lattice parameter of


ZnxCo1-xFe2O4
For x=0.1, Co0.9Zn0.1Fe2O4

(Zn2+ 3+
0.1 𝐹𝑒0.9 )A [Co2+ 3+ 2−
0.9 𝐹𝑒1.1 ]B𝑂4

(0 x0.1)+(5 x 0.9) ( 3x 0.9)+(1.1x5)

=4.5 B = 8.2 B

nB =8.2 B – 4.5B =3.7 B

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑥 𝑀𝑠
nB =
𝑁𝑥𝐵

235.263 𝑥 𝑀𝑠
3.7 =
6.023 𝑥1023 𝑥0.927𝑥10−20

Ms = 87.81 emu/gm

Lattice parameter

𝑟𝐴 = (0.1 x0.74) + (0.9 x0.645)= 0.6545 Å


1
𝑟𝐵 = 2 [( 0.9 x 0.745)+(1.1x 0.645]= 0.69 Å

8
ath=3√3 [(0.6545+1.32)+ √3 (0.69+1.32)]=8.3999 Å

The calculation for x=0.2 and 0.3 can be done similarly as that of x=0.1.

For x=0.2, 𝑛𝐵 = 4.4B , 𝑀𝑠 = 104.17 𝑒𝑚𝑢/𝑔𝑚 ,𝑎𝑡ℎ = 8.4012 Å

For x=0.3, 𝑛𝐵 = 5.1 B , 𝑀𝑠 = 120.37 𝑒𝑚𝑢/𝑔𝑚 ,𝑎𝑡ℎ = 8.40 25 Å


For x=0.4, Co0.6Zn0.4Fe2O4

(Zn2+ 3+
0.4 𝐹𝑒0.6 )A [Co2+ 3+ 2−
0.6 𝐹𝑒1.4 ]B𝑂4

(0 x0.4)+(5 x 0.6) ( 3x 0.6)+(1.4x5)

=3B = 8.8B

nB=8.8 B – 3 B = 5.8 B

The addition of Zn2+ should decrease the magnetization .The downturn of magnetization can
be explained by triangular arrangements of spins which was proposed by Yafet and Kittel. Y-
K angles are calculated using the formula : nB =MB cos𝛼𝑌−𝐾 – MA

For ( 𝛼𝑌−𝐾 = 20º)

nB =8.8 B cos𝛼𝑌−𝐾 – 3B = 5.266 B

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑥 𝑀𝑠
nB =
𝑁𝑥𝐵

for nB= 5.266B ; Ms= 123.95 emu/gm

for nB= 5.8 B; Ms= 136.523 emu/gm

Lattice parameter

𝑟𝐴 = (0.4 x0.74) + (0.6 x0.645)= 0.683 Å

1
𝑟𝐵 = 2 [( 0.6 x 0.745)+(1.4x 0.645]= 0.675 Å

8
ath=3√3 [(0.683+1.32)+ √3 (0.675+1.32)]=8.4038 Å

The calculation for x=0.5, 0.6, 0.7, 0.8 and 0.9 can be done similarly as that of x= 0.4.

For x=0.5

𝑛𝐵 = 6.5B , 𝑀𝑠 = 152.58 𝑒𝑚𝑢/𝑔𝑚 ,

𝛼𝑌−𝐾 = 30º, 𝑛𝐵 = 5.295B , 𝑀𝑠 = 124.67 𝑒𝑚𝑢/𝑔𝑚


𝑎𝑡ℎ = 8.4049 Å

For x=0.6

𝑛𝐵 = 7.2B , 𝑀𝑠 = 171.435 𝑒𝑚𝑢/𝑔𝑚 ,

𝛼𝑌−𝐾 = 40º, 𝑛𝐵 = 5.047B , 𝑀𝑠 = 118.155 𝑒𝑚𝑢/𝑔𝑚

𝑎𝑡ℎ = 8.4064 Å

For x=0.7

𝑛𝐵 = 7.9B , 𝑀𝑠 = 184.45 𝑒𝑚𝑢/𝑔𝑚 ,

𝛼𝑌−𝐾 = 60º, 𝑛𝐵 = 3.2 B , 𝑀𝑠 = 74.71 𝑒𝑚𝑢/𝑔𝑚

𝑎𝑡ℎ = 8.4076 Å

For x=0.8

𝑛𝐵 = 8.6 B , 𝑀𝑠 = 200.25 𝑒𝑚𝑢/𝑔𝑚 ,

𝛼𝑌−𝐾 = 70º, 𝑛𝐵 = 2.3 B , 𝑀𝑠 = 53.55 𝑒𝑚𝑢/𝑔𝑚

𝑎𝑡ℎ = 8.4089 Å

For x=0.9

𝑛𝐵 = 9.3 B , 𝑀𝑠 = 215.97 𝑒𝑚𝑢/𝑔𝑚 ,

𝛼𝑌−𝐾 = 80º, 𝑛𝐵 = 1.2 B , 𝑀𝑠 = 27.87 𝑒𝑚𝑢/𝑔𝑚

𝑎𝑡ℎ = 8.4103 Å

ZnFe2O4

It can be written as (Zn2+)A [2 Fe3+]BO4

(0 x1) (5x2)

=0 B =10B
Net Magnetic moment in Bohr magnetron nB = MB – MA= 10B

Ms= 231.6 emu/gm

Using Yafet-Kittel formula for 𝛼𝑌−𝐾 = 90º, nB =0

Ms = 0 emu/gm

𝑎𝑡ℎ = 8.4116 Å

Table 1 : Theoretical magnetic moments, saturation magnetizations and lattice parameters of

ZnxCo1-xFe2O4 ferrites

x Chemical 𝑛𝐵 𝑀𝑠 Yafet-Kittel Lattice parameters (Å)


formulae (emu/gm)
𝛼𝑌−𝐾 𝑛𝐵 𝑀𝑠 𝑟𝐴 𝑟𝐵 𝑎𝑡ℎ
(B)
0 CoFe2O4 3 70.78 - 3 70.78 0.645 0.695 8.3986
0.1 Co0.9Zn0.1Fe2O4 3.7 87.81 - 3.7 87.81 0.6545 0.69 8.3999
0.2 Co0.8Zn0.2Fe2O4 4.4 104.14 - 4.4 104.14 0.664 0.685 8.4012
0.3 Co0.7Zn0.3Fe2O4 5.1 120.37 - 5.1 120.37 0.6735 0.68 8.4025
0.4 Co0.6Zn0.4Fe2O4 5.8 136.523 20 5.266 123.95 0.683 0.675 8.4038
0.5 Co0.5Zn0.5Fe2O4 6.5 152.58 30 5.295 124.67 0.6925 0.67 8.4049
0.6 Co0.4Zn0.6Fe2O4 7.2 171.435 40 5.047 118.155 0.702 0.665 8.4064
0.7 Co0.3Zn0.7Fe2O4 7.9 184.45 60 3.2 74.71 0.7115 0.66 8.4076
0.8 Co0.2Zn0.8Fe2O4 8.6 200.25 70 2.3 53.55 0.721 0.655 8.4089
0.9 Co0.1Zn0.9Fe2O4 9.3 215.97 80 1.2 27.87 0.7305 0.65 8.4103
1 ZnFe2O4 10 231.6 90 0 0 0.74 0.645 8.4116

Figure 1, 2 and 3 represent the variation of lattice parameters, magnetic moment and saturation
magnetization with the replacement of Co by Zn in CoFe2O4
8.412

8.410 ZnxCo1-xFe2O4

Lattice parameter (Å) 8.408

8.406

8.404

8.402

8.400

8.398

0.0 0.2 0.4 0.6 0.8 1.0


Chemical composition(x)

Figure .1 Increment in lattice parameters with the doping of Zn in CoFe2O4


11

10 Traditional calculation
Using Yafet- Kittel'sformula
9

8
Magnetic moment (B)

6
𝑛𝐵

0.0 0.2 0.4 0.6 0.8 1.0


CoFe2O4 ZnFe2O4
Chemical composition (x)

Figure 2. Variation of magnetic moment with the doping of Zn in CoFe2O4


240

220 Traditional calculation


200 Using Yafet Kittel fromula
Saturation magnetization( emu/gm)
180

160

140

120

100

80

60

40

20

0.0 0.2 0.4 0.6 0.8 1.0


Chemical composition (x)

Figure 3 .Variation of saturation magnetization with the doping of Zn in CoFe2O4