brief review on the synthesis and microscopic...

International Journal of Control Theory and Applications275

Brief Review on the Synthesis and Microscopic Properties of Pure and Doped Manganese Ferrites

S. Yuvaraja, N. Manikandanb and G. Vinithac

a,bSchool of Advanced Sciences, VIT University, Chennai, India. cCorresponding author, School of Advanced Sciences, VIT University, Chennai, India. Email: [email protected]

Abstract: Background/Objectives: This paper gives a brief review on various synthesis methods employed in the synthesizing pure and doped manganese ferrites. The studies on properties of these particles have also been reviewed.Methods/Statistical analysis: Ferrites have found extensive usage in different fields due to their higher magnetic strength and larger electrical resistance. Reduction in size of these materials to the nanometer regime has expanded their domain of applications. Manganese ferrites remain one of the widely studied materials owing to their better magnetic properties. Size, structure, shape and subsequent applications of these materials depend on the synthesis procedures and precursor materials used.Keywords: Manganese ferrites, Microscopy, Particle size, Synthesis methods.

INtRoDuctIoN1. Magnetic materials have found immense applications in the field of electromagnetism. Most of these magnetic materials are basically metallic in nature with iron, cobalt and nickel being the prominent ones for the formation of strong magnets. Research carried out in subsequent years showed that these metallic/alloy materials could be replaced by magnetic oxides based on iron. Ferrites form a special group of these materials which possess higher magnetic properties along with lower electrical conductivity/higher electrical resistivity. Presence of these contrasting properties leads to the replacement of metallic magnetic materials in applications like transformer cores with these ferrites1-9.

Lodestone, or magnetite, was a naturally occurring iron ferrite which was well known before the advent of other iron oxide materials. These materials generally crystallize in the form of AB2O4 with A representing tetrahedral site and B octahedral site. A site is normally occupied by a divalent cation leading to the formation of spinel structure. These cations can be distributed among both A and B sites which can lead to the formation of inverse spinel or mixed spinel structures10-12.

International Journal of Control Theory and Applications

ISSN : 0974-5572

„ International Science Press

Volume 9 • Number 51 • 2016

S. Yuvaraj, N. Manikandan and G. Vinitha

International Journal of Control Theory and Applications 276

Pure and doped manganese ferrites has been an extensively studied ferrite material over past few decades. Manganese ferrites shows higher saturation magnetization and magnetic susceptibility leading to its application in wide variety of applications like microwave devices, magnetic storage etc. These ferrites are easy to synthesize, has good chemical stability and also eco-friendly leading to application in the field of disposal of environmental pollutants. In addition, the presence of multiple valence states of manganese has been utilized to make them as sensing agents13-25.

Tailoring the properties of materials could be achieved by a reduction in size of the materials to the nanometer regime which widens the scope of application of most of the materials26-28. The properties so obtained of nanophase materials depend on the synthesis methods, dopant atoms, size and morphology of the particles29-32. Over the years of extensive investigations, it has been shown that the synthesis method dictate the starting precursor materials for ferrite preparation which will define the ease or difficulty in the synthesis procedure. Also, the formation of pure or impure phase ferrite samples was also found to be dependent on synthesis procedures adopted. It has been shown that introduction of rare earth atoms like samarium improves the magnetic properties of host ferrites33. Similarly, doping the parent spinel ferrite with various metal ions leads to structural disorder and lattice strain, thereby improving the electrical and magnetic parameters34. Size reduction has been found to show variation in Neel temperature, coercivity, saturation magnetization etc35-39.

This review is an attempt to consolidate various synthesis methods alongwith the variety of precursors used for each method and the properties obtained employing different characterization techniques for pure and doped manganese ferrites. Comparison has been done in various possible ways to identify the quality of samples obtained through various methods and for various applications.

MateRIalS aND MethoDS2. Structurally perfect pure and doped MnFe2O4 nanocrystals were successfully prepared by various methods like standard ceramic technique40, auto-combustion14, co-precipitation13,41, sol-gel 41,42, hydrothermal13, solid state reaction43, thermal decomposition13, solvothermal method44, sonochemical technique45, microwave-assisted ball milling46, Sol-gel auto-combustion47,48 etc.

It has been found that every method has its own merits and demerits49-51. Following flow chart shows the various steps to be followed in the preparation of pure phase manganese ferrite nanocrystals through five different methods.

2.1. Standard ceramic techniqueA standard method which provides the possibility of self-assembly of nanoparticles into superstructures by finding their optimum thermodynamic condition52,53. In general, oxides like MnO2 and Fe2O3 were mixed stoichiometrically, ground to a very fine powder using an agate mortar and then compressed into pellet form under certain pressure.

The samples were sintered at certain temperature to obtain pure manganese ferrites. Quality and sintering temperature depends on the effectiveness of mixing of the precursor materials leading to smaller sized particles which could be achieved by milling40,52.

2.2. auto combustion MethodThis process is convenient, inexpensive, environment friendly and efficient for preparation of manganese ferrite nanoparitcles52. In this technique, stoichiometric amount of precursor salts and urea were mixed in an agate mortar.



Preparation Method

Standard

Ceramic40,52,53 Auto Combustion

55,56Co-Precipitation

13,41,57,58Sol-gel

62,63Citrate

53,64

Dissolve in deionizedwater and Mixing

Stirrer with Heat

Washing and Dryand Sintering

Mn Ferrites

Mn Dioxide, FerricOxide, Precipitating

Agent (NaOH)

Raw Materials

Mn Dioxide,Ferric Oxide

Mn Dioxide,Ferric Oxide,Fuel (Urea)

Mn Dioxide,Ferric Oxide,

Chelting Agent

Mn Dioxide,Ferric Oxide,

Citric Acid

Mixing, Grounded,Pressed to Pellet

Sintering

Mn Ferrites

Mixing, Thermolysis(500˚C for 30 min)

Sintering

Washing and Dry

Mn Ferrites

Mixing

Thermolysis

Sintering

Mn Ferrites

Dissolve in deionizedwater and Mixing

Evaporation

Sintering

Mn Ferrites

Figure 1: Flow chart of different preparation routes

Urea was added to the mixture as fuel and the mixture was transferred to a quartz crucible. A reaction occurs within the mixture leading to combustion which gets completed in a very short time of 3 to 5 minutes. Foamy and highly porous precursor mass was obtained which was collected and then powdered55,56. The ferrite powder was pre-sintered, pelletized and then sintered again at higher temperatures to yield pure manganese ferrites14. The pre-sintering and sintering temperatures again depend on the composition and precursor material chosen for particular cases.

2.3. co-precipitation MethodThis is a well known method used from earlier times that involves chemical co-precipitation of salts with a base leading to the formation of a precipitate containing all the components mixed at an ionic level13,41,57,58. Modifications were done to this method in order to improve the homogeneity of these particles. An aqueous solution of metal salt was precipitated with a strong base leading to the formation of hydroxide in the mixture which was oxidized by bubbling air through the suspension. Resultant fine grained homogenous ferrite sample was obtained as the final product by this wet chemical process53,59. Co-precipitation reaction involves the simultaneous occurrence of nucleation, growth, coarsening and agglomeration. After the initiation of precipitation, numerous small crystallites form initially due to nucleation which quickly agglomerate together to form thermodynamically



stable larger particles60. pH of the solution was altered to obtain suitable precipitate. The precipitate was then washed and filtered to get required manganese ferrite powder61.

2.4. Sol-gel MethodGood control of composition, purity, homogeneity, particle sizes and distribution can be obtained using sol-gel method62. An appropriate amount of manganese and iron nitrates along with citric acid (C6H8O7) was first dissolved in a medium like ethylene glycol and then small quantity of distilled water was added to this mixture. This mixture was subjected to vigorous stirring and the resulting solution was allowed to evaporate to form a gel. Heating and drying of this gel at temperature well above room temperature for different time intervals lead to the formation of different sized nanoparticles48,63.

2.5. citrate Precursor MethodDecomposed citrates could be used to obtain ultrafine particles at low temperatures53. Stoichiometric amount of ferric nitrate was dissolved in de-ionized water and mixed with an aqueous solution of citric acid in a 1:1 molar ratio of cation to citric acid. Stoichiometric amount of manganese nitrate was added dropwise under continuous stirring condition. The mixture was allowed to evaporate slowly and then dried along with stirring until brown agglomerate was observed. The obtained powder was heated at pelletized and sintered to obtain ferrite sample22,64.

StRuctuRal PRoPeRtIeS3.

3.1. Pure Manganese FerritesExtensive work has been done to establish relationships between particle size, structure, surface area and shape of pure and doped manganese ferrite nanoparticles24. As stated earlier, the properties of these materials are also sensitive to the preparation conditions and methods adopted. It has been found that even a single step variation affects structural properties leading to changes in various other properties. Table 1 summarizes the crystallite size variations depending on different synthesis methods adopted.

table 1 comparison of the properties of Mn ferrites synthesized by different approaches

S. No. Synthesis Procedure Sintering Temperature (°C) Crystal Size

(nm) Ref.

1 Bulk MnFe2O4 – – 652 Sonochemical 650-950 34-36 463 One-Pot 150 45 664 Solvothermal 140-180 4-6 675 Ceramic technique 900-1100 ~7000 686 Microwave assisted ball milling <100 20 697 Sol-gel auto combustion 350 30 708 Thermal decomposition 723-923 12-22 719 Co-precipitation method 600 26.53 7210 Spark-plasma sintering 700-900 0.3-1.2 µm 66

Identification of suitable sintering temperatures, raw materials and preparation technique decides the possibility of achieving phase pure MnFe2O4. It has been found that in the co-precipitation technique, pure phase manganese ferrites could be achieved at low temperature if chlorides were used as precursor materials. On the



other hand, if nitrates were used as precursor materials, then higher annealing temperatures becomes mandatory for the formation of pure phase.

A short analysis has been done in the following section concentrating on the co-precipitation technique. Table 2 shows briefly the conditions and the resultant crystallite sizes for different precursors.

table 2 Precursor materials and related experimental parameters for pure manganese ferrites synthesized

by chemical co-precipitation technique

S. No. Precursor Materials Heat Treatment Conditions Crystallite

Size (nm) Ref.

1 Manganese nitrate-[Mn(NO3)2]Ferric nitrate-[Fe(NO3)3]Sodium Hydroxide-[NaOH]

Pre Sintered - 600°C for 4 H,Finally sintered - 1200°C for 8 H (After making pellet)

72.5 14

2 Manganese (II) sulfate-[MnSO4]Iron (III) sulfate-[FeSO4]Sodium hydroxide-[NaOH]

1050 °C Under argon gas 80 61

3 Iron (III) chloride hexahydrate [FeCl3.6H2O]Manganese (II) chloride tetrahydrate [MnCl2.4H2O]Sodium hydroxide [NaOH]

80°C for 90 min90°C for 90 mincalcined at373 K (100 °C) for 2H473 K (200 °C) for 2H

515

200220

73

74

table 3 experimental methods and parameters for copper doped manganese ferrites

S. No. Synthesis Method Copper

Concentration (%)Sintering

Temperature (°C)Crystal Size

(nm)Lattice

Constant (Å) Ref.

1. Co-Precipitation 0.2 – 0.3 1350 - 8.452-8.45 780.4-0.5 1250 - 8.441-8.44

2. Auto Combustion 0.5 as-burnt 9 8.42 54600 16 8.41900 47 8.41

3. Evaporation 0.5 as-burnt 17 8.37 77600 28 8.39900 55 8.41

4. Reverse Micelle Process 0.0-0.5 - 4-22 - 795. Standard Ceramic 0.0-0.75 1200 - 2.59-2.55 806. Citrate precursor 0.2, 0.5, 0.8, 1.0 Various temp. 64

3.1.1. Metal NitratesMetal nitrates have been used widely to form manganese ferrites. In most of these cases, the crystalline single phase was formed at temperatures above 550°C. The batches were heated in air at 600°C for 4 h, then pelletized and finally sintered at 1200°C for longer time interval. Single phase with cubic spinel structure belonging to the FCC system was obtained by this method14. The samples which were pre-sintered at 900°C and subsequently calcined at the same temperature displayed single phase cubic spinel structure of MnFe2O4 along with two minor peaks of the a-Fe2O3 phase. The formation of small fraction of a-Fe2O3 phase was mainly due to the partial oxidation of spinel ferrites. Increase of oxidation atmosphere time interval at the same temperature led to the formation of higher peak intensities related to MnFe2O4 structure75.



table 4 experimental methods and parameters for cadmium doped manganese ferrites

S. No. Synthesis Method Cadmium



(nm)Lattice

Constant (Å) Ref.

1 Double Sintering Ceramic 0.2-0.8 1250 - 8.612-8.672 812 Hydrothermal 0.1,0.3 180 46-57 8.51-8.52 823 Co-precipitation 0.2 900 148 9.40 75

table 5 experimental methods and parameters for zinc doped manganese ferrites

S. No. Synthesis Methods Zinc



(nm)Lattice

Constant (Å) Ref.

1 Double Sintering Ceramic Technique

0.2-0.8 1250 - 8.528-8.582 81

2 Co-precipitation method 0.2 900 117.63 9.3955 753 Co-precipitation method 0.0-1.0 - 15.8-4.6 8.470-8.457 834 Solution combustion method 0.0-1.0 1000 25-35 8.432-8.372 84

table 6 experimental methods and parameters for nickel doped manganese ferrites

S. No. Synthesis Methods Nickel



(nm)Lattice

Constant (Å) Ref.

1 Auto-combustion 0.6 (50%, 75%, 100% fuel)

As-burnt 25-34 8.44-8.45 86600 52-58 8.45-8.46900 65-75 8.47

2 Ceramic method 0.3,0.5,0.7 1200 12-18 8.44 -8.33 90

table 7 experimental methods and parameters for cobalt doped manganese ferrites

S. No. Synthesis Methods Cobalt



(nm)Lattice

Constant (Å) Ref.

1 Simple evaporation 0.6 As-burnt 12 8.42 91600 23 8.43900 51 8.45

2 Polyol 0.8-1.0 - 5 - 4.8 8.37-8.39 923 Calcining precursor oxalates 0.5 800-950 23 - 39 ± 1.4 - 93

table 8 experimental methods and parameters for magnesium

doped manganese ferrites

S. No. Synthesis Method Magnesium


Temperature (˚C)Crystal Size

(nm)Lattice

Constant (Å) Ref.

1 Hydrothermal route 0.0-1.0 - 8.471-8.443 962 Co-precipitation 0-0.3 - 4-7 97

0-0.25 3-6 98



3.1.2. Metal SulfatesPure phase ferrites were obtained for the powders annealed at 1050°C in argon atmosphere when metal sulphates were used as starting materials. The peaks for as-prepared and 650°C annealed samples under air atmosphere were associated with manganese ferrite and possibly some traces of unknown extra peaks. Annealing in air did not lead to a single phase Mn ferrite. The improvements of the crystallographic and magnetic properties were due to the heat treatment under Argon atmosphere61.

3.1.3. Metal ChloridesChloride precursor materials were able to yield pure phase ferrite samples even for as-prepared samples, which did not involve any calcination. The as-prepared samples which were digested at 80°C and 90°C formed spinel structured MnFe2O4

76. It was observed that the spectrum for the undigested particles had two broad peaks without any structure. Digestion led to the formation of several peaks corresponding to MnFe2O4

73. The samples which were digested at lower temperatures did not yield single-phase spinel structure. Instead, it gave a mixture of MnFe2O4 and a-Fe2O3 phases76.

3.2. Doped Manganese Ferrites

3.2.1. Copper Doped Manganese FerritesVarious synthesis methods and the related parameters in terms of the experimental conditions has been given in the following table for copper doped manganese ferrites. It was observed that the standard ceramic technique and the co-precipitation method required the samples to be annealed at higher temperatures for suitable phase formation. In the reported auto-combustion and evaporation methods54,77 it was observed that the as-prepared samples were phase pure whereas samples subjected to annealing at higher temperatures led to the formation of secondary phases. On the other hand, samples formed by co-precipitation method showed dependence of sintering temperature on the concentration of copper atoms in deciding the phase purity of these samples78. Lattice constants were found to vary monotonically depending on the relative size difference between the dopant and the host manganese atoms.

Among various methods used to synthesize cadmium doped manganese ferrites, hydrothermal method is one among few which does not need the calcination of samples at higher temperatures for phase formation. Systematic study of Cd substituted MnFe2O4 samples showed the formation of single phase sample only until Cd concentration of 0.3. Equal concentrations of cadmium and manganese led to the formation of hexagonal phase of cadmium hydroxide with very weak peaks of MnFe2O4

81. Co-precipitation techniques used for the synthesis of this sample invariably requires annealing at higher temperatures, leading to the formation of secondary phases75.

Zinc doped manganese ferrites prepared by co-precipitation and solution combustion methods showed diametrically varying lattice constant values. Smaller size of zinc compared to manganese should have caused a monotonic decrease in lattice constant with the replacement of manganese by zinc atoms. Reported co-precipitated Zn-Mn-ferrite showed a fluctuating distribution of lattice constants attributing the reason to either the replacement of smaller Fe3+ ions by Zn2+ ions or to the partial migration of Zn2+ ions from A site to B site83. Solution combustion method showed a systematic decrease in lattice constant indicating the effect of synthesis procedure in deciding the lattice structure and formation of the required ferrite samples84,85.

Nickel doped manganese ferrites were synthesized by various methods. Auto-combustion method used showed the fuel concentration defines the crystallinity and the particle size of these materials. The presence of impure phase was found to depend only on the annealing temperature irrespective of the fuel ratio used86. It was



reported that 50% fuel ratio to be an optimum condition for achieving smaller sized samples. Ceramic method adopted showed the formation of spinel ferrite structure for varied nickel concentrations87-90.

3.2.2. Cobalt Doped Manganese FerritesCobalt doped manganese ferrites were found to form smaller sized particles compared to other mixed ferrites like ZnFe2O4, CuFe2O4, NiFe2O4

91 even for similar synthesis methods adopted92-95.

3.2.3. Magnesium Doped Manganese FerritesAs-prepared magnesium doped manganese ferrites obtained by co-precipitation method yielded pure phase samples and annealed samples led to the formation of impure phase similar to copper doped manganese ferrite across varied dopant concentrations. On the other hand, dependence on the concentration of dopant atoms was found on the phase purity of sample when hydrothermal synthesis method was considered96.

MIcRoScoPY4. Scanning Electron (SEM) and Transmission Electron (TEM) Microscopic techniques have been used extensively to identify the shape and particle size of nanomaterials. SEM is normally used to analyze the surface and shape of the formed particles. It has been reported that different synthesis methods adopted lead to the formation of different shapes and structures for both pure and doped ferrites. Pure MnFe2O4 sample synthesized by hydrothermal method was found to contain polycrystalline grains with average size of few hundred nanometers99 whereas sample synthesized by sol-gel auto combustion method showed heavily agglomerated spherical globules with size around 15 nm100. Uncalcined samples which were digested between 20°C and 70°C consisted of many nearly mono disperse nanospheres with average diameter of about 300 nm76.

The external morphology of the nano crystalline Mn-Cu ferrite nanoparticles annealed at 900°C clearly showed the agglomeration of primary nano particles to give large and irregular crystals due to the effect of annealing and the formation of impure phases54. The microstructures of the as prepared manganese ferrite sample by hydrothermal route without substitution of Cd led to the formation of quasi-spherical agglomerated particles with a quite uniform size distribution whereas the sample doped with 50% cadmium showed the existence of large crystals of hexagonal phase of cadmium hydroxide82. Similarly, the micrographs of Ni doped Mn ferrite showed agglomerates of spinel structures compared to fine particles in pure nickel ferrite101. Mn0.5Zn0.5Fe2O4 prepared by spray pyrolysis in nitrogen atmosphere consisted of regularly shaped spherical particles102. The morphology of the cobalt-manganese ferrites showed irregular and agglomerated particles91. Similar results were observed for other dopant like Mg also96.

TEM image of Mn ferrites indicated that the typical individual ferrite microsphere was a loose cluster which is composed by small nanocrystals in the size range around 8–12 nm. The selected-area electron diffraction (SAED) pattern showed that the diffraction spots were widened into narrow arcs, indicating the clusters were made up of many misaligned ferrite nanocrystals103-106 in agreement with the analysis of HRTEM. The d value of crystal plane (311) in TEM and characteristic peaks in XRD verifies the crystalline structure of MnFe2O4 nanocrystals19.

TEM image of the annealed sample of Mn-Cu ferrite have been found to be almost spherical with size in the range of 40 to 60nm54. The microstructures of the as-prepared Cd substituted manganese ferrite sample were found to have cubic shape with a quite uniform size distribution. It is consistent with the results of crystallite sizes obtained from XRD data82. Good crystallinity and particle size of Mn0.4Ni0.6Fe2O4 nanoparticles have been visualized through transmission electron microscope also in close agreement with the XRD measurement86.



Selected area electronic diffraction (SAED) pattern of Mn0.5Zn0.5Fe2O4 consisted of concentric rings with spots over the rings indicating the crystallinity of the samples84.

coNcluSIoN5. Pure and doped manganese ferrites nanoparticles were obtained by various methods that dictated the size, shape and structure of the final particles. The precursor materials determined the ease or difficultness in the formation of ferrite nanoparticles and the subsequent synthesis technique to be adopted for various materials. Samples annealed at higher temperature were invariably found to lead to impure phases in these materials. This review confined itself to the synthesis methods and conditions adopted for the formation of pure and doped manganese ferrite samples. Microscopic techniques alone were discussed to understand the different structures obtained based on the synthesis conditions and procedures.

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brief review on the synthesis and microscopic...

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