research article synthesis and characterization of lithium...

Hindawi Publishing CorporationIndian Journal of Materials ScienceVolume 2013 Article ID 910762 7 pageshttpdxdoiorg1011552013910762

Research ArticleSynthesis and Characterization of Lithium-SubstitutedCu-Mn Ferrite Nanoparticles

M A Mohshin Quraishi1 and M H R Khan2

1 Department of Physics Manarat Dhaka International College Dhaka 1212 Bangladesh2Department of Arts and Sciences Ahsanullah University of Science and Technology Dhaka 1208 Bangladesh

Correspondence should be addressed to M A Mohshin Quraishi mphysyahoocom

Received 5 July 2013 Accepted 29 August 2013

Academic Editors H Leiste and D L Sales

Copyright copy 2013 M A M Quraishi and M H R Khan This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

The effect of Li substitution on the structural and magnetic properties of Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(x = 000 010 020 030 040

and 044) ferrite nanoparticles prepared by combustion technique has been investigated Structural and surface morphology havebeen studied by X-ray diffractometer (XRD) and high-resolution optical microscope respectively The observed particle size ofvarious Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4is found to be in the range of 9 nm to 30 nm XRD result confirms single-phase spinel structure

for each composition The lattice constant increases with increasing Li content The bulk density shows a decreasing trend with LisubstitutionThe real part of initial permeability (1205831015840

119894) and the grain size (D) increase with increasing Li content It has been observed

that the higher the 1205831015840119894is the lower the resonance frequency in Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites is

1 Introduction

Ferrite nanoparticles have attracted a growing interest due totheir potential applications such as magnetic recording [1]storage [2] and biotechnology [3] In the most recent yearsthe interest in the use of nanoparticles in biomedical appli-cations has greatly increased [4 5] The size and compositionof nanoparticles influence the bio-application of themagneticnanoparticles [6] It is well known that the physical and chem-ical properties of the nanosized magnetic materials are quitedifferent from those of the bulk ones due to their surface effectand quantum confinement effectsThese nanoparticles can beobtained through precipitation of metallic salts in differentmedia as polymers [7] organic acid or alcohol [8] sugars [9]and so forth In particular sol-gel autocombustion thermaldecomposition hydrothermal ball milling reverse micellesynthesis solid-phase reaction thermally activated solid statereaction and pulsed laser deposition have been developed toprepare the single-domain MnFe

2O4nanoparticles [10ndash23]

Manganese ferrite (MnFe2O4) nanoparticles have become

very popular due to their wide range of magnetic applica-tions such as recording devices drug delivery ferrofluidbiosensors and catalysis [10 24ndash27] Recently Deraz and

Alarifi [28] have studied structural and magnetic propertiesof MnFe

2O4nanoparticles by combustion route Till now no

other report has been found in the literature for Li-dopedCu-Mn ferrite Lithium ferrites are low-cost materials whichare attractive formicrowave device applications Hence therehas been a growing interest in Li-substituted Cu-Mn ferritefor microwave applications and high permeability with lowmagnetic loss Therefore this paper is devoted to studythe effect of Li+ substitution on the physical and magneticproperties of Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites prepared by

combustion technique

2 Experimental

21 Sample Preparation and Characterization The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites were prepared by autocombustion

technique The analytical grade of Li(NO3)2MnCl

2sdot4H2O

Cu(NO3)2sdot3H2O and Fe(NO

3)3sdot9H2O was taken as raw

material and weighted according to the stoichiometricamount and then dissolved in ethanol The mixture wasplaced in a magnetic heating stirrer at 80∘C followed by anignition the combustion takes place within a few seconds

2 Indian Journal of Materials Science

and fine nanosized powders were precipitatedThese powderswere crushed and ground thoroughlyThe fine powders of thecomposition were then calcined at 900∘C for 5 h for the finalformation of Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites nanoparti-

cles Then the fine powders were granulated using polyvinylalcohol (PVA) as a binder and pressed uniaxially into disk-shaped (about 13mm outer diameter 15mmndash20mm thick-ness) and toroid-shaped (about 13mm outer diameter about65mm inner diameter and 2mm thickness) samples Thesamples prepared from each composition were sintered at1200∘C for 1 hour in air The temperature ranges for sinteringwas maintained at 5∘Cmin for heating and 10∘Cmin forcooling All sintered samples were polished and thermaletchingwas performed X-ray diffractionwas carried outwithan X-ray diffractometer (Model D8 Advance Bruker AXS)for each sample For this purpose monochromatic Cu-K

120572

radiation was used The lattice parameter for each peak ofeach sample was calculated by using the formula

1198860= 119889radicℎ2 + 1198962 + 1198972 (1)

where ℎ 119896 and 119897 are the indices of the crystal planesTo determine the exact lattice parameter for each sampleNelson-Riley method was used The Nelson-Riley function119865(120579) is given as

119865 (120579) =1

2[(

Cos2120579Sin 120579

) + (Cos2120579120579

)] (2)

The values of lattice constant ldquo119886rdquo of all the peaks for asample are plotted against 119865(120579) Then using a least-squarefit method exact lattice parameter ldquo119886

119900rdquo was determined The

point where the least-square fit straight line cuts the 119910-axis(ie at 119865(120579) = 0 or 120579 = 90∘) is the actual lattice parameter ofthe sample

The physical or bulk densities 120588119861of the samples were

determined by Archimedes principle with water mediumusing the following expression

120588119861=

119882120588

119882 minus1198821015840gcm3 (3)

where119882 is the weight of the sample in air1198821015840 is the weight ofthe sample in the water and 120588 is the density of water in roomtemperature

The theoretical density 120588th was calculated using thefollowing expression

120588th =8119872

1198731198601198863119900

gcm3 (4)

where119873119860is Avogadrorsquos number (602 times 1023molminus1) and119872 is

the molecular weightThe optical micrographs for various Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites have been taken by using high-resolution

optical microscope (Model NMM-800TRF) Average grainsizes of all samples were determined from optical micro-graphs by linear intercept technique [29] The frequency-dependent initial permeability for each sample wasmeasuredby using aWayne Kerr Impedance Analyzer (Model 6500B)

The complex permeability measurement on toroid-shapedsamples was carried out at room temperature in frequencyrange 10KHzndash100MHz Both the 1205831015840

119894and 12058310158401015840

119894of the complex

permeability were calculated using the following relations

1205831015840

119894=119871119904

1198710

12058310158401015840

119894= 1205831015840

119894tan 120575

(5)

where 119871119904is the self-inductance of the sample core and

1198710= 1205831199001198732

119878120587119889 is derived geometrically Here 1198710is the

inductance of the winding coil without the sample core 119873is the number of turns of the coil (119873 = 5) and 119878 is the area ofcross-section of the toroidal sample as follows

119878 = 119889 times ℎ (6)

where 119889 = (1198892minus 1198891)2 119889

1= inner diameter 119889

2= outer

diameter ℎ = Height and 119889 is the mean diameter of thetoroidal sample as follows

119889 =1198891+ 1198892

2 (7)

The Loss factor tan 120575 was determined from the ratio(= 120583101584010158401198941205831015840119894)

3 Results and Discussion

31 X-Ray Diffraction Analysis The XRD analysis was per-formed to verify the formation of spinel structure of var-ious Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites in which Mn2+ is

replaced with Li+ and Fe3+ The XRD patterns of these Li+-substituted Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4(with 119909 = 000 010

020 030 040 and 044) ferrites sintered at 1200∘C in airfor 1 h are shown in Figure 1 The patterns indicated thatthese materials have a well-defined single crystalline phaseand formation of cubic spinel structure for each compositionAnalyzing the XRD patterns it is observed that the positionsof the peaks comply with the reported value [30] and sometraces of raw materials were found for 119909 = 000 119909 = 010 and119909 = 020 and 119909 = 030)

32 Lattice Constant The values of lattice constant obtainedfrom each plane are plotted against Nelson-Riley function[31] The values of lattice constant were estimated from theextrapolation of these lines to 119865(120579) = 0 or 120579 = 90

∘ Itis noticed from Figure 2 that 119886

0increases with the increase

of Li+ content in Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(with 119909 = 000

010 020 030 040 and 044) ferrites Values of 1198860for

various Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites are presented in

Table 2 The increase in 1198860with Li content indicates that the

present system obeys Vegardrsquos law [32]This increase of 1198860can

be attributed to the ionic sizeThe ionic radius of Li+ (076 A)is greater than that ofMn2+ (067 A) [29 33]When the largerLi+and Fe3+ ions enter the lattice the unit cell expands whilepreserving the overall cubic symmetry

Indian Journal of Materials Science 3

20 30 40 50 60

MnO

(440

)

(511

)

(422

)

(400

)

(311

)

(220

)

Inte

nsity

(au

)

2120579 (deg)

Fe2O3

Fe2O3

Fe2O3

Fe2O3

x = 044

x = 040

x = 030

x = 020

x = 010

x = 000

LixCu012Mn088minus2xFe2+xO4

Figure 1 The X-ray diffraction patterns for various Li119909Cu012

Mn088minus2119909

Fe2+119909

O4sintered at 1200∘C

33 Average Particle Size The average particle size wasestimated by using Debye-Scherrer [34] formula from thebroadening of the highest intensity peaks (311) of XRDpatterns

119863 =09120582

120573 cos 120579 (8)

where 119863 is the average particle size 120582 is the wavelengthof the radiation used as the primary beam of Cu-K

120572(120582 =

154178 A) 120579 is the angle of the incident beam in degreeand 120573 is the full width at half maximum (FWHM) of thefundamental reflection (311) in radian of the FCC ferritesphase Debye-Scherer formula assumes approximation andgives the average particle size if the grain size distribution isnarrow and strain-induced effects are quite negligible

Figure 3 shows the XRD patterns of Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites sintered at 1200∘C for 1 h where (311) peak

is shown in expanded form to understand the variationof FWHM of the Bragg peaks with the Li content FromFigure 3 it is seen that the value of FWHM decreases withthe increase of lithium contentThe particle size of the sampleis inversely proportional to FWHM according to Debye-Scherrer formula The observed particle size is in the rangefrom 9 to 30 nm which has been listed in Table 1

34 Theoretical and Bulk Density The values of 120588th and 120588119861

for the various Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites (with 119909 =

000 010 020 030 040 and 044) are tabulated in Table 2It is noticed from Figure 4 that both 120588th and 120588119861 decrease withthe increase of Li substitution in Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4

ferrites for constant sintering temperatureThis phenomenoncould be explained in terms of the atomic weightThe atomicweight of Mn (5494 amu) is greater than that of combinedatomic weight of the Li (6941 amu) and Fe (55845 amu)[33]

35 Microstructure The optical micrographs of Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites (where 119909 = 000 119909 = 010 119909 = 020

119909=030119909=040 and119909=044) are shown in Figure 5 sintered

00 01 02 03 04 05

834

836

838

840

842

1860

1872

1884

1896

Li content x


Latti

ce co

nsta

nta

0(A

)

a0(A)

r-va

riant

(A)

r-variant (A)

Figure 2 Variation of lattice constant and 119903-variant with Li contentfor various Li

119909Cu012

Mn088minus2119909

Fe2+119909


345 350 355 360 365

Inte

nsity

(au

)

2120579 (deg)

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

Figure 3 XRD patterns of (311) peak with Li content for variousLi119909Cu012

Mn088minus2119909

Fe2+119909

O4nanoparticles

00 01 02 03 0442

45

48

51

54


Li content x

Den

sity120588

(gc

m3)

Ts = 1200∘C

120588th

120588B

Figure 4The variation of theoretical density and bulk density withLi content for various Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4


50120583m 50120583m

50120583m 50120583m

50120583m 50120583m

x = 000 x = 010

x = 020 x = 030

x = 040 x = 044

Figure 5 The optical micrographs of Li119909Cu012

Mn088minus2119909

Fe2+119909


at 1200∘CThe grain size (119863) is significantly dependent on Lisubstitution The 119863 increases with increasing Li substitutionfor fixed sintering temperature which is shown in Figure 5This is probably due to the lower melting temperature of Li(180∘C) compared toMn (1245∘C)The values of119863 for variousLi119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites are presented in Table 2

36 Complex Initial Permeability The compositional varia-tions of complex initial permeability spectra for the variousLi119909Cu012

Mn088minus2119909

Fe2+119909

O4samples sintered at 1200∘C are

shown in Figure 6 It is observed that the 1205831015840119894remains fairly

constant in the frequency range up to some critical frequencywhich is called resonance frequency 119891

119903 A sharp decrease

in 1205831015840119894and increase in 12058310158401015840

119894are observed above the 119891

119903 The

1205831015840

119894increases with the increase of Li+ content for various

Li119909Cu012

Mn088minus2119909

Fe2+119909

O4 On the other hand 119891

119903was

found to decrease with Li substitution It was observed that

1205831015840

119894of Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites sintered at 1200∘C

increases from 18 to 55 Figure 7 shows both 1205831015840119894and 119863 as a

function of Li content for various Li119909Cu012

Mn088minus2119909

Fe2+119909

O4

ferrites According to Globus and Duplex model [35] the1205831015840

119894can be explained as 1205831015840

119894= 119872

2

119904119863radic119870 where 119872

119904is

the saturation magnetization and 119870 is the magnetocrys-talline anisotropy constant This increase in permeability isexpected because grain size of all samples increases withLi content It is known that the mobility of domain walls isgreatly affected by the microstructure of ferrites Thereforein the present case variation of the initial permeability maybe influenced by its grain size

The variation of loss factor tan 120575 (= 120583101584010158401198941205831015840

119894) with

frequency for all samples has been studied Thevariation of initial loss with frequency for the variousLi119909Cu012

Mn088minus2119909

Fe2+119909

O4samples sintered at 1200∘C is

shown in Figure 8 At lower frequencies magnetic loss isobserved and remains constant up to a certain frequency


15

30

45

60

Frequency (Hz)104 105 106 107 108

120583998400 i

Ts = 1200∘C

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(a)

0

5

10

15

Frequency (Hz)106 107 108


120583998400998400 i

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(b)

Figure 6 The 1205831015840119894and 12058310158401015840

119894for various Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4

ferrites sintered at 1200∘C as function of frequency

Table 1 Particle size and FWHM of Li119909Cu012

Mn088minus2119909

Fe2+119909

O4

nanoparticles

x FWHM (in degree) Particle size (nm)000 0015379 94010 000733 19020 0006109 23030 0004712 30040 0004887 30044 0005411 27

9MHz this frequency limit depends upon the sinteringtemperatures The lag of domain wall motion with respect

00 01 02 03 04 05

20

30

40

50

60

0

55

110

165

220

275

Grain size


120583998400 i

120583998400

i

Gra

in si

ze (120583

m)

Li content x

Ts = 1200∘C

Figure 7 The 1205831015840119894and grain size with Li content for various

Li119909Cu012

Mn088minus2119909

Fe2+119909


00

01

02

03

04

Loss

fact

or

Frequency (Hz)


x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

Ts = 1200∘C

106 107 108

Figure 8 Loss factor as a function of frequency for variousLi119909Cu012

Mn088minus2119909

Fe2+119909


Table 2The lattice parameter density average grain size and initialpermeability of Li

119909Cu012

Mn088minus2119909

Fe2+119909


x 119886119900(A) 120588th (gcm

3) 120588119861

(gcm3) D (120583m) 1205831015840

119894(at 10 KHz)

000 83370 532 482 1792 18010 83615 515 462 19 22020 83746 502 458 39 33030 83866 490 444 92 39040 84024 476 441 14545 50044 84091 456 430 29545 55

to the applied magnetic field is responsible for magneticloss and this is accredited to lattice imperfections [36] Athigher frequencies a rapid increase in loss factor is observedA resonance loss peak is shown in this rapid increase ofmagnetic loss At the resonance maximum energy transferoccurs from the applied field to the lattice which results inthe rapid increases in loss factor


4 Conclusion

The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(119909 = 000 to 119909 = 044)

nanoparticles have been successfully synthesized by the com-bustion technique The observed particle size is in the rangefrom9 nm to 30 nmTheXRDpatterns confirm that the com-positions are single phase and form cubic spinel structureThe lattice parameter increases linearly with increasing Licontent and obeys Vegardrsquos law The study of microstructureshows that grain size increases with increasing Li contentThe bulk density decreases with increasing Li substitutionin Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites The real part of initial

permeability increases with increase of Li content for a fixedsintering temperature This result may be explained withthe help of average grain size The highest 1205831015840

119894was found

55 for 119909 = 044 which is three times greater than thatof parent composition It was also observed that the reso-nance frequency 119891

119903 and real part of initial permeability 1205831015840

119894

are inversely proportional which confirms Snoekrsquos relation1198911199031205831015840

119894= constant

Acknowledgments

The authors are grateful to the BUET authority for providingfinancial support for this research The authors are alsothankful to the authority of BCSIR for using their equipment

References

[1] M Suda M Nakagawa T Iyoda and Y Einaga ldquoReversiblephotoswitching of ferromagnetic FePt nanoparticles at roomtemperaturerdquo Journal of the American Chemical Society vol 129no 17 pp 5538ndash5543 2007

[2] B O Regan and M Gratzel ldquoA low-cost high-efficiency solarcell based on dye-sensitized colloidal TiO

2filmsrdquo Nature vol

353 pp 737ndash740 1991[3] M Shinkai ldquoFunctional magnetic particles for medical applica-

tionrdquo Journal of Bioscience and Bioengineering vol 94 no 6 pp606ndash613 2002

[4] C C Berry and A S G Curtis ldquoFunctionalisation of mag-netic nanoparticles for applications in biomedicinerdquo Journal ofPhysics D vol 36 no 13 article R198 2003

[5] S Mornet S Vasseur F Grasset and E Duguet ldquoMagneticnanoparticle design for medical diagnosis and therapyrdquo Journalof Materials Chemistry vol 14 no 14 pp 2161ndash2175 2004

[6] C Corot P Robert J M Idee and M Port ldquoRecent advancesin iron oxide nanocrystal technology for medical imagingrdquoAdvanced Drug Delivery Reviews vol 58 no 14 pp 1471ndash15042006

[7] J-F Berret N Schonbeck F Gazeau et al ldquoControlled clus-tering of superparamagnetic nanoparticles using block copoly-mers design of new contrast agents for magnetic resonanceimagingrdquo Journal of the American Chemical Society vol 128 no5 pp 1755ndash1761 2006

[8] C Sun R Size and M Zhang ldquoFolic acid-PEG conjugatedsuperparamagnetic nanoparticles for targeted cellular uptakeand detection byMRIrdquo Journal of BiomedicalMaterials ResearchA vol 78 no 3 pp 550ndash557 2006

[9] R Y Hong B Feng L L Chen GH Li Y Zeng andD GWeildquoSynthesis characterization and MRI application of dextran-coated Fe

3O4magnetic nanoparticlesrdquo Biochemical Engineering

Journal vol 42 no 3 pp 290ndash300 2008[10] N M Deraz and S Shaban ldquoOptimization of catalytic surface

and magnetic properties of nanocrystalline manganese ferriterdquoJournal of Analytical and Applied Pyrolysis vol 86 pp 173ndash1792009

[11] M A Ahmed N Okasha and M M El-Sayed ldquoEnhancementof the physical properties of rare-earth-substituted Mn-Znferrites prepared by flash methodrdquo Ceramics International vol33 no 1 pp 49ndash58 2007

[12] Q M Wei J-B Li Y-J Chen and Y-S Han ldquoX-ray studyof cation distribution in NiMn

1minus119909Fe2minus119909

O4ferritesrdquo Materials

Characterization vol 47 no 3-4 pp 247ndash252 2001[13] MHMahmoudHHHamdeh J CHoM J OrsquoShea and J C

Walker ldquoMoessbauer studies of manganese ferrite fine particlesprocessed by ball-millingrdquo Journal of Magnetism and MagneticMaterials vol 220 no 2 pp 139ndash146 2000

[14] M Muroi R Street P G McCormick and J AmighianldquoMagnetic properties of ultrafine MnFe

2O4powders prepared

bymechanochemical processingrdquo Physical Review B vol 63 no18 Article ID 184414 2001

[15] C Li and Z J Zhang ldquoSize-dependent superparamagneticproperties of Mn spinel ferrite nanoparticles synthesized fromreversemicellesrdquoChemistry ofMaterials vol 13 no 6 pp 2092ndash2096 2001

[16] M HMahmoud C MWilliams J Cai I Siu and J CWalkerldquoInvestigation of Mn-ferrite films produced by pulsed laserdepositionrdquo Journal of Magnetism and Magnetic Materials vol261 no 3 pp 314ndash318 2003

[17] C Alvani G Ennas A La Barbera GMarongiu F Padella andF Varsano ldquoSynthesis and characterization of nanocrystallineMnFe

2O4 advances in thermochemical water splittingrdquo Inter-

national Journal of Hydrogen Energy vol 30 no 13-14 pp 1407ndash1411 2005

[18] D Carta M F Casula A Falqui et al ldquoA structural and mag-netic investigation of the inversion degree in ferrite nanocrys-tals MFe

2O4(M = Mn Co Ni)rdquo Journal of Physical Chemistry

C vol 113 no 20 pp 8606ndash8615 2009[19] Y Liu Y Zhang J D Feng C F Li J Shi andR Xiong ldquoDepen-

dence of magnetic properties on crystallite size of CoFe2O4

nanoparticles synthesised by auto-combustion methodrdquo Jour-nal of Experimental Nanoscience vol 4 no 2 pp 159ndash168 2009

[20] C Cannas A Musinu D Peddis and G Piccaluga ldquoSynthesisand characterization of CoFe

2O4nanoparticles dispersed in a

silica matrix by a sol-gel autocombustion methodrdquo Chemistryof Materials vol 18 no 16 pp 3835ndash3842 2006

[21] C Cannas A Falqui A Musinu D Peddis and G PiccalugaldquoCoFe

2O4nanocrystalline powders prepared by citrate-gel

methods synthesis structure andmagnetic propertiesrdquo Journalof Nanoparticle Research vol 8 no 2 pp 255ndash267 2006

[22] LJ Zhao HJ Zhang Y Xing et al ldquoStudies on the magnetismof cobalt ferrite nanocrystals synthesized by hydrothermalmethodrdquo Journal of Solid State Chemistry vol 181 no 2 pp 245ndash252 2008

[23] Q Liu JH Sun HR Long XQ Sun XJ Zhong and ZXu ldquoHydrothermal synthesis of CoFe

2O4nanoplatelets and

nanoparticlesrdquoMaterials Chemistry and Physics vol 108 no 2-3 pp 269ndash273 2008

[24] S R Ahmed S B Ogale G C Papaefthymiou R Rameshand P Kofinas ldquoMagnetic properties of CoFe

2O4nanoparticles


synthesized through a block copolymer nanoreactor routerdquoApplied Physics Letters vol 80 no 9 pp 1616ndash1618 2002

[25] I Brigger C Dubernet and P Couvreur ldquoNanoparticles incancer therapy and diagnosisrdquoAdvancedDrugDelivery Reviewsvol 54 no 5 pp 631ndash651 2002

[26] R Arulmurugan G Vaidyanathan S Sendhilnathan and BJeyadevan ldquoMn-Zn ferrite nanoparticles for ferrofluid prepa-ration study on thermal-magnetic propertiesrdquo Journal of Mag-netism and Magnetic Materials vol 298 no 2 pp 83ndash94 2006

[27] J B Haun T J Yoon H Lee and R Weissleder ldquoMagneticnanoparticle biosensorsrdquoWiley Interdisciplinary Reviews vol 2no 3 pp 291ndash304 2010

[28] N M Deraz and A Alarifi ldquoControlled synthesis physic-ochemical and magnetic properties of nano-crystalline Mnferrite systemrdquo International Journal of Electrochemical Sciencevol 7 pp 5534ndash5543 2012

[29] M I Mendelson ldquoAverage grain size in polycrystalline ceram-icsrdquo Journal of the American Ceramic Society vol 52 no 8 pp443ndash446 1969

[30] C Rath S Anand R P Das et al ldquoDependence on cationdistribution of particle size lattice parameter and magneticproperties in nanosize Mn-Zn ferriterdquo Journal of AppliedPhysics vol 91 no 4 article 2211 2002

[31] J B Nelson and D P Riley ldquoAn experimental investigation ofextrapolation methods in the derivation of accurate unit-celldimensions of crystalsrdquo Proceedings of the Physical Society vol57 no 3 pp 160ndash177 1945

[32] L Vegard ldquoThe constitution of mixed crystal and the spaceoccupied by atomrdquo Zeitschrift fur Physik no 17 pp 17ndash26 1921

[33] M J Winter University of Sheffield Yorkshire UK 1995ndash2006httpwwwwebelementscom

[34] B D Cullity Elements of X-Ray Diffraction Addison-WesleyReading Mass USA 3rd edition 1972

[35] A Globus P Duplex and G M Guyot ldquoDetermination ofinitial magnetization curve from crystallites size and effectiveanisotropy fieldrdquo IEEE Transactions on Magnetics vol 7 no 3pp 617ndash622 1971

[36] J L Snoek ldquoDispersion and absorption in magnetic ferrites atfrequencies above one Mcsrdquo Physica vol 17 no 4 pp 207ndash2171948

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and fine nanosized powders were precipitatedThese powderswere crushed and ground thoroughlyThe fine powders of thecomposition were then calcined at 900∘C for 5 h for the finalformation of Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites nanoparti-

cles Then the fine powders were granulated using polyvinylalcohol (PVA) as a binder and pressed uniaxially into disk-shaped (about 13mm outer diameter 15mmndash20mm thick-ness) and toroid-shaped (about 13mm outer diameter about65mm inner diameter and 2mm thickness) samples Thesamples prepared from each composition were sintered at1200∘C for 1 hour in air The temperature ranges for sinteringwas maintained at 5∘Cmin for heating and 10∘Cmin forcooling All sintered samples were polished and thermaletchingwas performed X-ray diffractionwas carried outwithan X-ray diffractometer (Model D8 Advance Bruker AXS)for each sample For this purpose monochromatic Cu-K

120572

radiation was used The lattice parameter for each peak ofeach sample was calculated by using the formula

1198860= 119889radicℎ2 + 1198962 + 1198972 (1)

where ℎ 119896 and 119897 are the indices of the crystal planesTo determine the exact lattice parameter for each sampleNelson-Riley method was used The Nelson-Riley function119865(120579) is given as

119865 (120579) =1

2[(

Cos2120579Sin 120579

) + (Cos2120579120579

)] (2)

The values of lattice constant ldquo119886rdquo of all the peaks for asample are plotted against 119865(120579) Then using a least-squarefit method exact lattice parameter ldquo119886

119900rdquo was determined The

point where the least-square fit straight line cuts the 119910-axis(ie at 119865(120579) = 0 or 120579 = 90∘) is the actual lattice parameter ofthe sample

The physical or bulk densities 120588119861of the samples were

determined by Archimedes principle with water mediumusing the following expression

120588119861=

119882120588

119882 minus1198821015840gcm3 (3)

where119882 is the weight of the sample in air1198821015840 is the weight ofthe sample in the water and 120588 is the density of water in roomtemperature

The theoretical density 120588th was calculated using thefollowing expression

120588th =8119872

1198731198601198863119900

gcm3 (4)

where119873119860is Avogadrorsquos number (602 times 1023molminus1) and119872 is

the molecular weightThe optical micrographs for various Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites have been taken by using high-resolution

optical microscope (Model NMM-800TRF) Average grainsizes of all samples were determined from optical micro-graphs by linear intercept technique [29] The frequency-dependent initial permeability for each sample wasmeasuredby using aWayne Kerr Impedance Analyzer (Model 6500B)

The complex permeability measurement on toroid-shapedsamples was carried out at room temperature in frequencyrange 10KHzndash100MHz Both the 1205831015840

119894and 12058310158401015840

119894of the complex

permeability were calculated using the following relations

1205831015840

119894=119871119904

1198710

12058310158401015840

119894= 1205831015840

119894tan 120575

(5)

where 119871119904is the self-inductance of the sample core and

1198710= 1205831199001198732

119878120587119889 is derived geometrically Here 1198710is the

inductance of the winding coil without the sample core 119873is the number of turns of the coil (119873 = 5) and 119878 is the area ofcross-section of the toroidal sample as follows

119878 = 119889 times ℎ (6)

where 119889 = (1198892minus 1198891)2 119889

1= inner diameter 119889

2= outer

diameter ℎ = Height and 119889 is the mean diameter of thetoroidal sample as follows

119889 =1198891+ 1198892

2 (7)

The Loss factor tan 120575 was determined from the ratio(= 120583101584010158401198941205831015840119894)

3 Results and Discussion

31 X-Ray Diffraction Analysis The XRD analysis was per-formed to verify the formation of spinel structure of var-ious Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites in which Mn2+ is

replaced with Li+ and Fe3+ The XRD patterns of these Li+-substituted Li

119909Cu012

Mn088minus2119909

Fe2+119909

O4(with 119909 = 000 010

020 030 040 and 044) ferrites sintered at 1200∘C in airfor 1 h are shown in Figure 1 The patterns indicated thatthese materials have a well-defined single crystalline phaseand formation of cubic spinel structure for each compositionAnalyzing the XRD patterns it is observed that the positionsof the peaks comply with the reported value [30] and sometraces of raw materials were found for 119909 = 000 119909 = 010 and119909 = 020 and 119909 = 030)

32 Lattice Constant The values of lattice constant obtainedfrom each plane are plotted against Nelson-Riley function[31] The values of lattice constant were estimated from theextrapolation of these lines to 119865(120579) = 0 or 120579 = 90

∘ Itis noticed from Figure 2 that 119886

0increases with the increase

of Li+ content in Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(with 119909 = 000

010 020 030 040 and 044) ferrites Values of 1198860for

various Li119909Cu012

Mn088minus2119909

Fe2+119909

O4ferrites are presented in

Table 2 The increase in 1198860with Li content indicates that the

present system obeys Vegardrsquos law [32]This increase of 1198860can

be attributed to the ionic sizeThe ionic radius of Li+ (076 A)is greater than that ofMn2+ (067 A) [29 33]When the largerLi+and Fe3+ ions enter the lattice the unit cell expands whilepreserving the overall cubic symmetry


20 30 40 50 60

MnO

(440

)

(511

)

(422

)

(400

)

(311

)

(220

)

Inte

nsity

(au

)

2120579 (deg)

Fe2O3

Fe2O3

Fe2O3

Fe2O3

x = 044

x = 040

x = 030

x = 020

x = 010

x = 000



Mn088minus2119909

Fe2+119909



119863 =09120582

120573 cos 120579 (8)


120572(120582 =



Mn088minus2119909

Fe2+119909





Mn088minus2119909

Fe2+119909



119909Cu012

Mn088minus2119909

Fe2+119909

O4



Mn088minus2119909

Fe2+119909

O4ferrites (where 119909 = 000 119909 = 010 119909 = 020


00 01 02 03 04 05

834

836

838

840

842

1860

1872

1884

1896

Li content x


Latti

ce co

nsta

nta

0(A

)

a0(A)

r-va

riant

(A)

r-variant (A)


119909Cu012

Mn088minus2119909

Fe2+119909


345 350 355 360 365

Inte

nsity

(au

)

2120579 (deg)

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000


Mn088minus2119909

Fe2+119909

O4nanoparticles

00 01 02 03 0442

45

48

51

54


Li content x

Den

sity120588

(gc

m3)

Ts = 1200∘C

120588th

120588B


119909Cu012

Mn088minus2119909

Fe2+119909

O4


50120583m 50120583m

50120583m 50120583m

50120583m 50120583m

x = 000 x = 010

x = 020 x = 030

x = 040 x = 044


Mn088minus2119909

Fe2+119909



Mn088minus2119909

Fe2+119909



Mn088minus2119909

Fe2+119909







119903 The

1205831015840


Li119909Cu012

Mn088minus2119909

Fe2+119909


119903was


1205831015840

119894of Li119909Cu012

Mn088minus2119909

Fe2+119909




Mn088minus2119909

Fe2+119909

O4



119894= 119872

2

119904119863radic119870 where 119872

119904is



119894) with


Mn088minus2119909

Fe2+119909




15

30

45

60

Frequency (Hz)104 105 106 107 108

120583998400 i

Ts = 1200∘C

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(a)

0

5

10

15



120583998400998400 i

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(b)

Figure 6 The 1205831015840119894and 12058310158401015840


119909Cu012

Mn088minus2119909

Fe2+119909

O4



Mn088minus2119909

Fe2+119909

O4

nanoparticles



00 01 02 03 04 05

20

30

40

50

60

0

55

110

165

220

275

Grain size


120583998400 i

120583998400

i

Gra

in si

ze (120583

m)

Li content x

Ts = 1200∘C


Li119909Cu012

Mn088minus2119909

Fe2+119909


00

01

02

03

04

Loss

fact

or

Frequency (Hz)


x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

Ts = 1200∘C

106 107 108


Mn088minus2119909

Fe2+119909



119909Cu012

Mn088minus2119909

Fe2+119909


x 119886119900(A) 120588th (gcm

3) 120588119861

(gcm3) D (120583m) 1205831015840

119894(at 10 KHz)

000 83370 532 482 1792 18010 83615 515 462 19 22020 83746 502 458 39 33030 83866 490 444 92 39040 84024 476 441 14545 50044 84091 456 430 29545 55



4 Conclusion

The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(119909 = 000 to 119909 = 044)


Mn088minus2119909

Fe2+119909



119894was found



119894


119894= constant

Acknowledgments


References






















2O4powders prepared























2O4nanoparticles






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




20 30 40 50 60

MnO

(440

)

(511

)

(422

)

(400

)

(311

)

(220

)

Inte

nsity

(au

)

2120579 (deg)

Fe2O3

Fe2O3

Fe2O3

Fe2O3

x = 044

x = 040

x = 030

x = 020

x = 010

x = 000



Mn088minus2119909

Fe2+119909



119863 =09120582

120573 cos 120579 (8)


120572(120582 =



Mn088minus2119909

Fe2+119909





Mn088minus2119909

Fe2+119909



119909Cu012

Mn088minus2119909

Fe2+119909

O4



Mn088minus2119909

Fe2+119909

O4ferrites (where 119909 = 000 119909 = 010 119909 = 020


00 01 02 03 04 05

834

836

838

840

842

1860

1872

1884

1896

Li content x


Latti

ce co

nsta

nta

0(A

)

a0(A)

r-va

riant

(A)

r-variant (A)


119909Cu012

Mn088minus2119909

Fe2+119909


345 350 355 360 365

Inte

nsity

(au

)

2120579 (deg)

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000


Mn088minus2119909

Fe2+119909

O4nanoparticles

00 01 02 03 0442

45

48

51

54


Li content x

Den

sity120588

(gc

m3)

Ts = 1200∘C

120588th

120588B


119909Cu012

Mn088minus2119909

Fe2+119909

O4


50120583m 50120583m

50120583m 50120583m

50120583m 50120583m

x = 000 x = 010

x = 020 x = 030

x = 040 x = 044


Mn088minus2119909

Fe2+119909



Mn088minus2119909

Fe2+119909



Mn088minus2119909

Fe2+119909







119903 The

1205831015840


Li119909Cu012

Mn088minus2119909

Fe2+119909


119903was


1205831015840

119894of Li119909Cu012

Mn088minus2119909

Fe2+119909




Mn088minus2119909

Fe2+119909

O4



119894= 119872

2

119904119863radic119870 where 119872

119904is



119894) with


Mn088minus2119909

Fe2+119909




15

30

45

60

Frequency (Hz)104 105 106 107 108

120583998400 i

Ts = 1200∘C

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(a)

0

5

10

15



120583998400998400 i

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(b)

Figure 6 The 1205831015840119894and 12058310158401015840


119909Cu012

Mn088minus2119909

Fe2+119909

O4



Mn088minus2119909

Fe2+119909

O4

nanoparticles



00 01 02 03 04 05

20

30

40

50

60

0

55

110

165

220

275

Grain size


120583998400 i

120583998400

i

Gra

in si

ze (120583

m)

Li content x

Ts = 1200∘C


Li119909Cu012

Mn088minus2119909

Fe2+119909


00

01

02

03

04

Loss

fact

or

Frequency (Hz)


x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

Ts = 1200∘C

106 107 108


Mn088minus2119909

Fe2+119909



119909Cu012

Mn088minus2119909

Fe2+119909


x 119886119900(A) 120588th (gcm

3) 120588119861

(gcm3) D (120583m) 1205831015840

119894(at 10 KHz)

000 83370 532 482 1792 18010 83615 515 462 19 22020 83746 502 458 39 33030 83866 490 444 92 39040 84024 476 441 14545 50044 84091 456 430 29545 55



4 Conclusion

The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(119909 = 000 to 119909 = 044)


Mn088minus2119909

Fe2+119909



119894was found



119894


119894= constant

Acknowledgments


References






















2O4powders prepared























2O4nanoparticles






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




50120583m 50120583m

50120583m 50120583m

50120583m 50120583m

x = 000 x = 010

x = 020 x = 030

x = 040 x = 044


Mn088minus2119909

Fe2+119909



Mn088minus2119909

Fe2+119909



Mn088minus2119909

Fe2+119909







119903 The

1205831015840


Li119909Cu012

Mn088minus2119909

Fe2+119909


119903was


1205831015840

119894of Li119909Cu012

Mn088minus2119909

Fe2+119909




Mn088minus2119909

Fe2+119909

O4



119894= 119872

2

119904119863radic119870 where 119872

119904is



119894) with


Mn088minus2119909

Fe2+119909




15

30

45

60

Frequency (Hz)104 105 106 107 108

120583998400 i

Ts = 1200∘C

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(a)

0

5

10

15



120583998400998400 i

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(b)

Figure 6 The 1205831015840119894and 12058310158401015840


119909Cu012

Mn088minus2119909

Fe2+119909

O4



Mn088minus2119909

Fe2+119909

O4

nanoparticles



00 01 02 03 04 05

20

30

40

50

60

0

55

110

165

220

275

Grain size


120583998400 i

120583998400

i

Gra

in si

ze (120583

m)

Li content x

Ts = 1200∘C


Li119909Cu012

Mn088minus2119909

Fe2+119909


00

01

02

03

04

Loss

fact

or

Frequency (Hz)


x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

Ts = 1200∘C

106 107 108


Mn088minus2119909

Fe2+119909



119909Cu012

Mn088minus2119909

Fe2+119909


x 119886119900(A) 120588th (gcm

3) 120588119861

(gcm3) D (120583m) 1205831015840

119894(at 10 KHz)

000 83370 532 482 1792 18010 83615 515 462 19 22020 83746 502 458 39 33030 83866 490 444 92 39040 84024 476 441 14545 50044 84091 456 430 29545 55



4 Conclusion

The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(119909 = 000 to 119909 = 044)


Mn088minus2119909

Fe2+119909



119894was found



119894


119894= constant

Acknowledgments


References






















2O4powders prepared























2O4nanoparticles






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




15

30

45

60

Frequency (Hz)104 105 106 107 108

120583998400 i

Ts = 1200∘C

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(a)

0

5

10

15



120583998400998400 i

x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

(b)

Figure 6 The 1205831015840119894and 12058310158401015840


119909Cu012

Mn088minus2119909

Fe2+119909

O4



Mn088minus2119909

Fe2+119909

O4

nanoparticles



00 01 02 03 04 05

20

30

40

50

60

0

55

110

165

220

275

Grain size


120583998400 i

120583998400

i

Gra

in si

ze (120583

m)

Li content x

Ts = 1200∘C


Li119909Cu012

Mn088minus2119909

Fe2+119909


00

01

02

03

04

Loss

fact

or

Frequency (Hz)


x = 010

x = 020

x = 030

x = 040

x = 044

x = 000

Ts = 1200∘C

106 107 108


Mn088minus2119909

Fe2+119909



119909Cu012

Mn088minus2119909

Fe2+119909


x 119886119900(A) 120588th (gcm

3) 120588119861

(gcm3) D (120583m) 1205831015840

119894(at 10 KHz)

000 83370 532 482 1792 18010 83615 515 462 19 22020 83746 502 458 39 33030 83866 490 444 92 39040 84024 476 441 14545 50044 84091 456 430 29545 55



4 Conclusion

The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(119909 = 000 to 119909 = 044)


Mn088minus2119909

Fe2+119909



119894was found



119894


119894= constant

Acknowledgments


References






















2O4powders prepared























2O4nanoparticles






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




4 Conclusion

The Li119909Cu012

Mn088minus2119909

Fe2+119909

O4(119909 = 000 to 119909 = 044)


Mn088minus2119909

Fe2+119909



119894was found



119894


119894= constant

Acknowledgments


References






















2O4powders prepared























2O4nanoparticles






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials
























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



research article synthesis and characterization of lithium...

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