Chapter 5
Synthesis of MgNiZnFe2O4 And its
Characterization
___________________________________________________________
In this chapter detail flow chart of the SOL-GEL method is shown. List of the raw
materials is mention in detail with their chemical name; chemical formula and molecular
weight. Details of all chemicals are given with all information. Chemical reaction
equations for all combinations are written in detail. Calculations for all combinations are
written in detail with their weights.
___________________________________________________________
5.1 Introduction:
Metallic ferrites are professionally significant samples since of their splendid electrical
properties & magnetic properties [1-3]. Preparation of nano-sized magnetized corpuscles is
earning attention in substance treating techs & in production of fresh substances. Preparation of
MgFe2O4 nanoparticles is significant for magnetic property, especially super-paramagnetic
behaviour & super-paramagnetic grains, & those may utilized towards dissimilar application.
These nano-sized magnetic grains shows attractive property that may be utilized in dissimilar
application such as, new pigments ,ferrofluids, high density recording, magnetic refrigerators &
high frequency devices, [4-8]. Cations Mg2+ & Fe3+ are unevenly allotted between tetrahedral
(A) & octahedral (B) lattice site & allocation is dependent on temperature [9]. In current study
fresh preparation of Mg0.7-xNixZn0.3Fe2O4 nanoferriteparticles utilizing low temperature autocombustion sol-gel procedure is reported. Magnetic natures of nanoparticles utilized for purpose
depend critically on sizing, figure & pureness of nanoferriteparticles. To examine this behavior
result of forming temperature & Ni2+ density is scientifically learned in Mg-Ni-Zn-Fe spinel
nanoferrite matter. Substitution of Mg2+ (0.66 Å) with Ni2+ (0.69 Å) may bring very important
varies in structural, magnetic orderings & cation distribution in spinel structure of substances.
SOL-GEL Method
5.2 flow chart for synthesis of MgNiZnFe2O4 nanoferrites.
Mg (NO3)2.
Ni (NO3)2.
Zn (NO3)2
Fe (NO3)3.
6H2O in
50ml Water
6H2O in
50ml Water
xH2O in 50ml
9H2O in
50ml Water
Water
Citric Acid (C6H8O7)
80oC for 20 min pH maintained
to 7, 100oC for 4-4.5 hrs
Ammonia
Liquid
Sintered at 400oC & 7000C for 2 hrs
Mg (0.7-x) Zn0.3
NixFe2O4 .xH2O
Mg (0.7-x) Zn0.3
NixFe2O4
XRD, SEM, FTIR
5.3 Procedure for the synthesis of MgNiZnFe2O4 by using “Low temperature Sol-Gel
method”:
The powders for x=.2, .4, .6 are prepared by auto- combustion sol gel technique. Chemicals
utilized for the powders are Nickel nitrate [Ni (No3)26H2o], magnesium nitrate [Mg (No3)26H2o],
Zinc nitrate [Zn (No3)26H2o], citric acid [C6H8O7H2O]Ferric nitrate [Fe2 (No3)9H2o]. These
chemicals were analytical grade. All were dissolved in process were conducted in air
atmospheric state in absent of shelter of inert gases. Metallic nitrates are dissolve collectively in
lower limit quantity of purified water to get apparent solvent. Aquas solvent of citric acid
mingled with metallic nitrate solvent. Then Ammonia solvents were contributed to set PH 7.
Then solvent is kept upon to magnetic stirrer on uninterrupted moving by magnetic needle on
1000c. For the duration of vaporization solvent became gummy and finally whole water is
withdrawn from combination. Then the gummy gel got frothing. Later little minuets gel
automatically combusted & fires on burning flints. The decay chemical reaction should not finish
prior to all citrate composite were wiped out. Auto- burning was finished in a minute giving
brown colored ash named as precursor. As cooked nanopowders of the materials is formed at
4000c and 7000c for 2 hours to get the final product. Samples are in powder form for XRD
investigation. Partly the ferritepowder was XRD studied by Philips x-ray diffraction
spectrometer (model 3710) utilizing CuK radiation (=1.5406). Powder XRD studies (x-ray)
have been conveyed out on the sintered samples at 4000c and 7000c for Mg0.5 Ni0.2 Zn0.3 Fe2O4,
Mg0.3 Ni0.4 Zn0.3 Fe2O4, Mg0.1 Ni0.6 Zn0.3Fe2O4. The dried gel powder is amorphous. The
crystalline size of nanoparticles was calculated by scherrer equation allowed that nanocrystalline
dimension is fewer than 100nanometer. d is mean crystalline size vertical to reflecting stage.
λ,wavelength of x-ray. K ,fixed near to units is concerned both to nanocrystalline pattern & to
the path is define i.e. ratio of the peak area to peak maximum.
The proportions of Magnesium nitrate, Zinc nitrate, Ferric nitrate & Nickel nitrate were
taken as per the stoichiometric ratios. The requisite quantity of Citric acid is added to a known
amount of these nitrates. The nitrate solution was formed by mixing all these nitrates in 170180ml water. Citric acid (which acts as a reducing agent) of the respective proportion was
contributed in this solvent. The mixture is stirred at 80oC for 20 minutes.
Due to reduction reaction the pH of the mixture changes and drops below than 7. To
maintain the pH and to make solution neutral, Ammonia liquid (33%) is then added till pH
increases to 7. After maintaining pH of the mixture, the mixture is heated and stirred
continuously at 100oC for 4-4.5 hours. After these hours the reaction turns and auto-combustion
takes place. The mixture is turns into gel, which further burns and turned into ash (in powder
form of MgNiZnFe2O4). This ash is first crush well and then sintered in a heating furnace at
400oC continuously for 4 hours. The heating rate of the furnace (Muffel furnace Regulator with
Pyrometer Watt-1600, Temp.-9000c, Size 22x10x10 Lab-Hosp.) was maintained constant at
5oC/min until the temperature reaches to 400oC then the temperature of furnace at 400oC kept
constant for 2 hours. [10-13]
The sintering process gives us a fine nano-powder of MgNiZnFe2O4. This powder is then
taken for different characterization techniques, viz: XRD, SEM, TEM, TGDTA, and FTIR
5.4 Raw Materials/Chemicals Used:
Name of Chemical
Chemical Formula
Weight of Molecule
Magnesium Nitrate
Mg(NO3)2.6H2O
256.41
Zinc nitrate
Zn( NO3)2xH2O
189.400
Nickel Nitrate
Ni(NO3)2.6H2O
290.79
Ferric Nitrate
Fe(NO3)3.9H2O
440.00
Citric Acid
C6H8O7
192.12
Table: 5.2(a): List of chemicals
5.5 Material Explanation:
5.5 (a) Magnesium Nitrate:
It is a hydroscopic salted which have chemical expression Mg (NO3)2. In atmosphere it
rapidly makes Hexahydrate Mg (NO3)2.6H2O and molar weight of 256.41 gm/ml. It is extremely
dissolvable with ethanol & water.
Molecular Formula
Mg(NO3)2.6H2O
Molecular Weight
256.41gm/ml
Melting Point
88.9oC
Appearance
White Crystalline Solid
Solubility in Water
125 gm/100ml
5.5(b) Zinc nitrate:
Zinc nitrate is a extremely hydrophilic material that generally cooked by fading out zinc in
nitric acid. It may be utilized as a mordant in coloring. e.g.Zn (NO3)2 + Na2CO3 → ZnCO3 + 2
NaNO3. substances /Conditions to keep off are: organic materials, reducing agents,metal
powders, cyanides, heat and flame,
sodium hypophosphite, phosphorus, tin(IV) chloride,
thiocyanates, sulfur & carbon,.
Molecular Formula
Zn( NO3)2xH2O
Molecular Weight
189.400 gm/ml
Melting Point
110 °C (anhydrous)
Appearance
colorless, deliquescent crystals
solvability in Water
327 g/100 mL, 40 °C (trihydrate)
5.5(c) Nickel Nitrate:
It is a chemical complex have molecular expression Ni (NO3)2. Nickel Nitrate is usually
encountered in Hexahydrate form. The formula for Hexahydrate form is scripted in 2 paths Ni
(H2O) 6(NO3)2 & Ni (NO3)2.6H2O .
Molecular Formula
Ni(NO3)2.6H2O
Molecular Weight
290.79 gm/ml
Melting Point
56.7 oC
Appearance
Emerald Green Hydroscopic Solid
Solubility in Water
94.2 gm/100ml
5.5(d) Ferric Nitrate:
Ferric Nitrate or Iron (III) Nitrate is a chemical complex have molecular formula Fe
(NO3)3, as it is hydrophilic. It is normally detected in its non-hydrate appearance Fe
(NO3)3.9H2O. in which it fleshes colorless - pale violet crystals.
Molecular Formula
Fe(NO3)3.9H2O
Molecular Weight
440.00 gm/ml
Melting Point
47.2 oC
Appearance
Pale Violet Crystal
Solubility in Water
Very Soluble
5.5(e) Citric Acid:
It is weakly natural acid. It is a raw conservative/ preservative& utilized for contribute sour
or acidic, cakes, soft drinks and taste to foods. It may be utilized as naturally dangerous irritation
to the skin and possible minor skin burns.
Molecular Formula
C6H8O7
Molecular Weight
192.12 gm/ml
Melting Point
153oC
Appearance
White Crystalline Solid
Solubility in Water
73 gm/100ml
5.6 Measurement of weight for MgNiZnFe2O4 nanoferrite material.
SET 1
For x=0.0
Chemical Reaction: for x=0.0
.7 Mg (NO3)2.6H2O +.3 Zn (NO3)2xH2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .7Zn.3Fe2O4
100oC for 4-4.5 hrs
SET II for x=0.0
Chemical Reaction: for x=0.0
.7 Mg (NO3)2.6H2O + 0.3 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .7Ni0.3Fe2O4
100oC for 4-4.5 hrs
SET III for x=0.0
Chemical Reaction: for x=0.0
.3 Mg (NO3)2.6H2O + 0.7 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .3Ni0.7Fe2O4
100oC for 4-4.5 hrs
5.6(a) Weight of Chemicals and Materials used for synthesis: Set No.I,Set No.II,Set No. III
Ni
Final
Mg
Zn
Product
(NO3)2.6H2O (NO3)2H2O
(10 gm)
(gm)
(gm)
Fe
C6H8O7
(NO3)2.6H2O (NO3)3.9H2O (gm)
(gm)
(gm)
X=0.0
8.45
2.67
0.00
38.05
27.14
X=0.0
8.53
0.000
4.14
38.42
29.97
X=0.0
3.43
0.000
9.08
36.07
28.14
SET NO. 2
Chemical Reaction: for x=0.2
.5 Mg (NO3)2.6H2O +.3 Zn (NO3)2xH2O +
0.2 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .5Zn.3Ni0.2Fe2O4
100oC for 4-4.5 hrs
Chemical Reaction: for x=0.4
.3 Mg (NO3)2.6H2O +.3 Zn (NO3)2xH2O +
0.4 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .3Zn.3Ni0.4Fe2O4
100oC for 4-4.5 hrs
Chemical Reaction: for x=0.6
.1 Mg (NO3)2.6H2O +.3 Zn (NO3)2xH2O +
0.6 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .1Zn.3Ni0.6Fe2O4
100oC for 4-4.5 hrs
5.6(b) Weight of Chemicals and Materials used for synthesis: Set no. 2
Final
Mg
Product
Zn
Ni
(NO3)2.6H2O (NO3)2H2O
(10 gm)
(gm)
(gm)
Fe
C6H8O7
(NO3)2.6H2O (NO3)3.9H2O (gm)
(gm)
(gm)
X= .2
5.85
2.60
2.65
36.89
26.31
X= .4
3.40
2.51
5.14
35.75
25.50
X= .6
1.10
2.43
7.49
34.69
24.74
SET NO.3
Chemical Reaction: for x=0.2
.5 Mg (NO3)2.6H2O +.2 Zn (NO3)2xH2O +
0.3 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .5Zn.2Ni0.3Fe2O4
100oC for 4-4.5 hrs
Chemical Reaction: for x=0.4
.3 Mg (NO3)2.6H2O +.4 Zn (NO3)2xH2O +
0.3 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .3Zn.4Ni0.3Fe2O4
100oC for 4-4.5 hrs
Chemical Reaction: for x=0.6
.1 Mg (NO3)2.6H2O +.6 Zn (NO3)2xH2O +
0.3 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .1Zn.6Ni0.3Fe2O4
100oC for 4-4.5 hrs
5.6(c) Weight of Chemicals and Materials used for synthesis: Set no. 3
Final
Mg
Product
Zn
Ni
(NO3)2.6H2O (NO3)2H2O
(10 gm)
(gm)
(gm)
Fe
C6H8O7
(NO3)2.6H2O (NO3)3.9H2O (gm)
(gm)
(gm)
X= .2
5.86
2.724
3.99
36.99
28.865
X= .4
3.39
5.248
3.848
35.641
27.808
X= .6
1.091
7.598
3.714
34.39
26.836
SET NO. 4
Chemical Reaction: for x=0.2
.3 Mg (NO3)2.6H2O +.2 Zn (NO3)2xH2O +
0.5 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .3Zn.2Ni0.5Fe2O4
100oC for 4-4.5 hrs
Chemical Reaction: for x=0.4
.3 Mg (NO3)2.6H2O +.4 Zn (NO3)2xH2O +
0.3 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .3Zn.4Ni0.3Fe2O4
100oC for 4-4.5 hrs
Chemical Reaction: for x=0.6
.3 Mg (NO3)2.6H2O +.6 Zn (NO3)2xH2O +
0.1 Ni (NO3)2.6H2O + 2 Fe (NO3)7 H2O + 3 C6H8O7
Mg .3Zn.6Ni0.1Fe2O4
100oC for 4-4.5 hrs
5.6(d) Weight of Chemicals and Materials used for synthesis: Set no. 4
Final
Mg
Product
Zn
Ni
(NO3)2.6H2O (NO3)2H2O
(10 gm)
(gm)
(gm)
Fe
C6H8O7
(NO3)2.6H2O (NO3)3.9H2O (gm)
(gm)
(gm)
X= .2
3.41
2.640
6.453
35.863
27.981
X= .4
3.39
5.251
3.850
35.65
27.820
X= .6
3.37
4.984
1.275
35.438
25.278
x=0.2
x=0.4
3000
2000
(100)
(220)
2500
INTENSITY (A.U)
1800
INTENSITY(A.U)
1600
(422)
1400
1200
(420)
(211)
(222)
2000
1500
(111)
(221)
(400)
(100)
(411)
1000
1000
800
20
30
40
50
60
2 THETA(DEGREE)
70
80
500
20
30
40
50
60
2 THETA (D EG REE)
70
80
X=0.6
2200
(1 1 0 )
2000
INTENSITY(A.U)
1800
1600
((2
221)
1400
1200
(41 0 )
(21 0 )
(1 1 1 )
1000
800
600
20
30
40
50
60
70
80
2 T H E T A (D E G R E E )
Fig.5.7 (a) XRD of MgNiZnFe2O4
Fig.5.7 (b) crystalline size with Ni content
X=0.2
Fig. 5.7(b).Variation in the lattice
as function of X-Value 400 0c
Fig.5.7 (b) X-ray density against X
X=0.4
parameter
value
X=0.6
Fig.5.7 (d) IR spectra of MgNiZn
(440)
(333)
(422)
(311)
(400)
IR of MgNiZnFe2O4 ferrite
(a)
Intensity (Arb. Units)
(220)
Fig.5.7(c) SEM of MgNiZnFe2O4 ferrite
(b)
(c)
(d)
(e)
(f)
20
30
40
50
60
70
80
5.25
o
26
400 C
5.20
5.15
22
(dx)
5.10
8.40
5.05
8.39
8.38
5.00
8.37
4.95
(a)
8.36
8.35
4.90
0.2
0.4
2+
Ni Concentration'x'
0.6
5.25
30
28
o
700 C
26
5.20
(t)
5.15
24
(dx)
22
8.40
5.10
5.05
8.39
8.38
5.00
8.37
4.95
(a)
8.36
8.35
4.90
0.2
0.4
2+
Ni Concentration'x'
0.6
X-ray density (dx)
(t)
24
Lattice constant (a) and Crystallite size (t)
28
X-ray density (dx)
Lattice constant (a) and Crystallite size (t)
2 θ (Degree)
2.20
N
4.50
2.15
4.45
4.40
2.10
4.35
2.05
4.30
4.25
2.00
4.20
4.10
0.2
0.3
Ni
0.4
2+
0.5
0.6
obs
1.95
4.15
Observed magneton number (nB )
Neel's magneton number (nB )
4.55
1.90
concentration 'x'
5.7 Conclusion:
The Sol-gel
gel technique is suitable for manufacture of MgNiZnFe2O4 nanoparticles. In this
work, we have presented the preparation
preparationof MgNiZnFe2O4 nanoferriteparticles
particles employing SolGel & auto-combustion route form
forming particles in range 21.439-28.863 nm by changing
chang
the
proportions of Mg and Ni.. The crystal structure and plane calculations were done using XRD
method.
Particle sizing of nanoparticles
anoparticles as calculated
lculated by using the Scherer’sformula.
Scherer’s
The
particle size was found to be changing as the proportions of Mg and Ni as x varies as 0.2, 0.4 and
0.6.. Additional advantage of the Sol
Sol-Gel
Gel method is that chemicals used for synthesis of
nanoparticles
ticles are easily available.
References
1.
J. Smit H. P. J. Wijin, Ferrites, Philips Technical Library, 1959.
2.
S. W. Lee, S. H. Yoon, S. Y. An, W. C. Kim, Chul Sung Kim, J. Magnetics, 4, (1999)
115.
3.
Maheshkumar L. Mane, V. N. Dhage, R. Sundar, K. Ranganathan, S. M. Oak, D. R.
Shengule, K. M. Jadhav, Appl. Surf. Sci. 257 (2011) 8511.
4.
E. M. M. Ibrahim, Appl. Phys. A 89, (2007) 203.
5.
M.A. Ahmed, Samiha T. Bishay, S.I. El-dek, G. Omar, J. Alloys Compd., 509 (2011) 805
6.
Xiangyu Hou, Jing Feng, Xiaohan Liu, Yueming Ren, Zhuangjun Fan, Milin Zhang, J.
Colloid Interface Sci., 353 (2011) 524.
7.
C. Venkatarajua, G. Sathishkumar, K. Sivakumar, J. Alloys Compd., 498 (2010) 203
8.
S.C. Watawe, U.A. Bamne, S.P. Gonbare, R.B. Tangsali, Mater. Chem. Phys. 103 (2007)
323.
9.
C. J. Kriesman, S. E. Harrison, Phys. Rev. 103 (1956) 857.
10. Ni, Zn/SiO2 Ferrites Nanocomposites prepared by an Improved Sol-Gel Method and their
Characterization. Journal of Optoelectronics and Advanced Materials. Vol. 7, No. 2, April
2005, Pg. 607-614.
11. Influence of Substitutional and Sintering Aids on Structural and Electromagnetic
Properties of NiCuZn Ferrite. By Pradip Kumar Roy. Department of Ceramic Engineering
National Institute of Technology, Rourkela, Orissa. January, 2009.
12. Synthesis and Characterization of Multiferroic Composite (Barium Titanate Nickel
Ferrite) By Solid State Route. By Anurag Kumar. Department of Ceramic Engineering
National Institute of Technology, Rourkela, Orissa. May, 2010.
13. Corriu, R.J.P, Leclercq. D.: Recent Development of Molecular Sol-gel process. Angew.
Chem. Int. Ed. 35, 1420-1436. 1996.