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Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

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Journal of Magnetism and Magnetic Materials


journal homepage: www.elsevier.com/locate/jmmm

Research articles

Study of structural, morphological and magnetic properties of Ag substituted T


cobalt ferrite nanoparticles prepared by honey assisted combustion method
and evaluation of their antibacterial activity
M.K. Satheeshkumara, E. Ranjith Kumarb, , Ch. Srinivasc, , N. Suriyanarayanand, , M. Deeptyc,
⁎ ⁎ ⁎

C.L. Prajapate, T.V. Chandrasekhar Raoe, D.L. Sastryf


a
Department of Physics, SriGuru Institute of Technology, Coimbatore 641110, Tamil Nadu, India
b
Department of Physics, Dr. N.G.P. Institute of Technology, Coimbatore 641048, Tamil Nadu, India
c
Department of Physics, Sasi Institute of Technology & Engineering, Tadepalligudem 534101, Andhra Pradesh, India
d
Department of Physics, Government College of Technology, Coimbatore 641 013, Tamil Nadu, India
e
Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, Maharashtra, India
f
Department of Physics, Andhra University, Visakhapatnam 530 003, Andhra Pradesh, India

ARTICLE INFO ABSTRACT

Keywords: Pure and Ag substituted cobalt ferrite nanoparticles (NPs) having the composition (1−x)CoFe2O4: xAg
Nanoparticles (x = 0.0, 0.2) were synthesized by a novel honey assisted combustion method in order to investigate their
Honey assisted synthesis structural and magnetic properties along with their antibacterial activity. XRD patters confirm the spinel phase
Structural analysis of CoFe2O4 and the presence of silver (Ag) nanoparticles in the spinel network. The incorporation of Ag in
Magnetic properties
CoFe2O4 spinel structure enhanced the size of the unit cell, resulting to higher value of lattice parameter (a)
compared to the pure CoFe2O4. The sintering process promoted the growth of the crystallite sizes (D). The
crystallite sizes of the synthesized and annealed powders were found in the range of 24–41 nm. From the EDX
studies, it seemed that the distribution of Ag nanoparticles was non-uniform. The saturation magnetization
(Ms) and coercivity (Hc) of the powders were influenced by annealing as well as with the substitution of Ag.
The highest value of saturation magnetization (60 emu/g) was obtained by the CoFe2O4 nanoparticles with the
coercivity value 1358 Oe. The saturation magnetization and coercivity of Ag doped CoFe2O4 were less than
that of pure CoFe2O4. The present cobalt ferrite nanoparticles and Ag doped cobalt ferrite nanoparticles have
shown good antibacterial activities. But Ag doped cobalt ferrite nanoparticles seems to be the potential can-
didates for effective antibacterial activity. The structural and magnetic results along with the results of an-
tibacterial activities are reported in the present manuscript.

1. Introduction ferrite NPs. But honey assisted combustion route has been believed to
be reliable to synthesize ultrafine ferrite NPs with narrow size dis-
In recent years, the research towards the magnetic NPs is of growing tribution [4,5]. Therefore, honey assisted combustion method has been
interest due to their potential utility in biomedicine applications. The adopted to prepare un-doped and Ag doped cobalt ferrite NPs.
functionalization of ferrite NPs can be found in a wide variety of ap- Even now, the fundamental research on spinel nanoparticles has
plications including biomedical applications like targeted drug de- been explored due to their versatile utility as photo catalysts in waste
livery, cancer treatment through hyperthermia, magnetic resonance water treatment as well as for their antibacterial activities. Bacterial
imaging, etc. [1–3]. The physical properties of ferrite nanoparticles are microbes E. Coli, S. Auresus can be frequently found in waste water,
very important to find the suitability for application. These properties flood water that are responsible for skin diseases. In particular, Candide
are mainly structure sensitive like the size and shape of the NPs as well microbe species are the human effective microorganisms causing in-
as processing conditions adopted for the preparation of ferrite nano- fections to nails, skin and mucosal surfaces. Silver (Ag) is a well-known
particles. Therefore, to attain definite recital, different wet chemical chemical agent which can affectively useful for antibacterial activity. In
methods as well as physical methods have been reported to produce the recent studies, silver (Ag) substituted and silver (Ag) coated ferrite


Corresponding authors.
E-mail addresses: ranjueaswar@gmail.com (E.R. Kumar), srinivas.chintoju75@gmail.com (C. Srinivas), nsuri22@gmail.com (N. Suriyanarayanan).

https://doi.org/10.1016/j.jmmm.2018.09.039
Received 23 August 2018; Received in revised form 6 September 2018; Accepted 8 September 2018
Available online 08 September 2018
0304-8853/ © 2018 Elsevier B.V. All rights reserved.
M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

nanoparticles were prepared in order to understand and improve the concentrated (100–500 mg) CoFe2O4 and AgCoFe2O4 nanoparticles
antibacterial activity of silver (Ag). Okasha et al. [6] experimented on sonicated in distilled water were pipetted on to individual inoculated
the effect of Ag doping in MgFe2O4 and reported a development in its agar plates and then incubated at 37 °C for 24 h before that the mi-
electrical and thermal conductivity. Kooti et al. [7] studied the biolo- croorganisms were cultured into nutrient broth medium and incubated
gical activity of AgCoFe2O4 nanocomposite. CoFe2O4 is a famous spinel at 37 °C for 2 to 5 h. Each strain was swabbed uniformly on to agar
ferrite which has reasonable saturation magnetization, high coercivity plates and 6 mm diameter wells were made in to which nanoparticles
and very high magneto-crystalline anisotropy. It can be found in bio- were loaded. The standard antibiotic streptomycin was also loaded as
medical applications like magnetic hyperthermia, targeted drug de- control to monitor any contamination during testing. Zones of inhibi-
livery and bactericides [8–10].The substitution of Ag in CoFe2O4 spinel tion surrounding the coated samples were measured by vernier caliper
structure or coating of Ag to CoFe2O4 ferrite nanoparticles provides a as a parameter of antibacterial property of the synthesized CoFe2O4 and
new composite material possessing good physical properties and anti- the AgCoFe2O4.
microbial active nature.
NPs with antibacterial activity can be found in huge applications 3. Results and discussion
like food processing and packaging, textile industry, biomedical de-
vices and water disinfection [11–13]. Among the various ferrites, 3.1. X-Ray diffraction studies
cobalt and Ag doped cobalt ferrite is of special class of interest due to
their unique physical, magnetic properties along with their wider XRD technique has been used to confirm the formation of phase in
scope of biomedical applications. Therefore, in the present study, as-burnt and annealed samples of cobalt and Ag doped cobalt ferrite
honey assisted combustion route has been adopted to prepare CoFe2O4 NPs. The respective XRD patterns are depicted in Fig. 2. The diffraction
and Ag doped CoFe2O4NPs with a chemical equation (1–x) CoFe2O4: peaks identified at the diffraction angles nearer to 30.19°, 35.55°,
xAg (x = 0.0, 0.2), assuming an advancement in the biological ac- 37.15°, 43.24°, 53.34°, 57.14°, 62.69° and 74.03o in all XRD patterns are
tivity. The present work deals with the structural, morphological and indexed with the miller indices (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2),
magnetic characterization of undoped and Ag doped CoFe2O4 NPs (5 1 1), (4 4 0) and (5 3 3). These are consistent with the JCPDS card no.
synthesized and it also aims to identify the action of these NPs in 75-0894 belonging to Fd3m space group with cubic spinel structure.
suitable biological applications. The diffraction peaks in the patterns (c) and (d) are noticed nearly at
the diffraction angles 38.09°, 44.39oand 64.69°, and are labeled as
2. Experimental procedure and characterization techniques (1 1 1), (2 0 0) and (2 2 0) comparing with the silver X-ray spectrum.
This observation confirms the presence of silver (Ag) nanoparticles in
2.1. Sample preparation the spinel ferrite network. The indexed diffraction planes are consistent
with JCPDS card no.004-0783 belonging to Fm3m space group with
Analytical grade cobalt nitrate (Co(NO3)26H2O), silver nitrate (Ag cubic structure. An interesting observation has been made from the
(NO3)2) and ferric nitrate (Fe(NO3)29H2O) are used as precursors to XRD patterns. The pure cobalt ferrite (CoFe2O4) both as-burnt and
synthesize CoFe2O4 and Ag doped CoFe2O4 ferrite NPs. These materials annealed samples seem to be free from the formation of secondary
are weighed in stoichiometric amounts along with freshly extracted phases, where in the silver (Ag) substituted cobalt ferrite secondary
honey from bees foraged on eucalyptus trees. In this typical experiment, phases of α–Fe2O3 (JCPDS card no.87-1166) are found which are in-
solutions of 0.5mol Co(NO3)26H2O, 1mol Fe(NO3)29H2O were slowly dexed in the XRD patterns. Generally, the methods of preparation,
added (1:2 ratio) to the honey solution (30 ml of fresh honey +20 ml of nature of additives, and optimum conditions for the preparation of
distilled water). They severely mixed for 1 h and finally ferrite powder ferrites are the factors that predominately affect the spinel structure of
was obtained by heating the mixed solution to 100 °C. The obtained ferrites and the formation of secondary phases. The literature reports
ferrite powder was milled in an agate mortar into a fine powder and a [14] disclose that the formation of secondary phases in Mn-ferrite and
portion of the powder was heat treated at 600 °C in the air atmosphere. Mn-substituted ferrites are phenomenal due to oxidation of Mn2+which
The same method was repeated to prepare Ag doped CoFe2O4 NPs (0.1 depends upon the local oxygen environment. A comprehensive analysis
mol Ag(NO3)2 + 0.4 mol Co(NO3)26H2O). The as prepared samples and of the formation of these secondary phases in different ferrite systems
sintered samples are characterized for structural, magnetic and anti- was reported in our previous publication [15]. In the present ferrite
bacterial studies. The pictorial diagram of method preparation is shown systems, the presence of Ag in the spinel structure seems to be affecting
in Fig. 1. the Fe3+ and O2– environments resulting to the formation of secondary
phases. The lattice constant (a) for cubic spinel structure was calculated
2.2. Characterization techniques using the formula [16]

X-ray diffractograms are obtained using Rigaku X-ray diffractometer a = d h2 + k 2 + l2 (1)


(Model ULTIMA III) with Cu-Kα(λ = 0.15406 nm) radiation as a target. where h, k, l = Miller indices, θ = Bragg angles and d = interplanar
JEOL 5600LV scanning electron microscope was employed to study spacing which can be calculated from the Bragg’s law 2dsinθ =λ.
the morphology of the samples through SEM pictures and composi- The crystallite sizes (D) of the samples were calculated using the
tional analysis through EDX. Debye-Scherrer formula[16]
TEM micrographs and selected-area electron diffraction (SAED)
k
have been recorded with the help of Technai G20-stwin HRTEM D=
cos (2)
working at an accelerating voltage of 200 kV.
Lakeshore model 7410 Vibrational Sample Magnetometer was used where β = full width at half maxima (FWHM) in radians, and k = shape
to obtain the hysteresis loops at room temperature. factor taken as 0.89.
The calculated values of lattice parameter (a) and crystallite size (D)
2.3. Antibacterial test for these samples are listed in Table 1.It was observed that the lattice
parameter of pure CoFe2O4 and Ag doped CoFe2O4 has been increased
Antibiotic susceptibility tests for the CoFe2O4 and the Ag doped with the heat treatment which is ascribed to the expansion of the unit
CoFe2O4 were carried out against Staphylococcus aureus (ATCC 25923); cell. Moreover, the lattice parameter of Ag doped CoFe2O4 (8.3877 Å) is
Escherichia coli (ATCC 25922) and Candida ablicans (ATCC 10231) using greater than that of un-doped CoFe2O4 (8.3721 Å). This may be due to
well diffusion method on Mueller–Hinton agar plates. The various the change of cations’ distribution occurred due to the substitution of

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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

Fig. 1. Schematic diagram of honey assisted combustion method.

Table 1
Structural and magnetic properties of (1–x)CoFe2O4: xAg (x = 0.0, 0.2) -
Sample A (as burnt CoFe2O4), Sample B (annealed CoFe2O4), Sample C(as burnt
Ag-CoFe2O4) and Sample D (annealed Ag-CoFe2O4).
Samples a D Ms Hc Mr S = Mr/Ms
(Å) (nm) (emu/g) (Oe) (emu/g)

Sample A 8.3721 24.1 48 1428.2 17.6 0.37


Sample B 8.4646 40.9 60 1358.1 23.7 0.39
Sample C 8.3877 27.5 31 648.1 9.1 0.29
Sample D 8.4795 39.3 38 721.7 11.7 0.31

doped CoFe2O4 are 24.1 nm and 40.9 nm. The crystallite sizes of the
prepared and the annealed Ag doped CoFe2O4 are 27.5 nm and 39.3 nm.
The improvement of crystallinity of ferrite NPs has been clearly iden-
tified by increasing the sharpness of the diffraction peaks under an-
nealing treatment which can be expected due to Oswald ripening. It was
observed that the crystallite size of ferrite NPs in the prepared Ag doped
CoFe2O4 is greater than that of the prepared un-doped CoFe2O4.
Whereas, the crystallite size of ferrite NPs in the annealed Ag doped
CoFe2O4 is less than that of the annealed un-doped CoFe2O4. With the
heat treatment, the size of Ag nanoparticles is increased. These bigger
Ag nanoparticles in the annealed Ag doped CoFe2O4 may be acted as
resistive centers at the grain boundaries to obstruct the release of sur-
face energy needed for the crystallite growth.

3.2. Energy Dispersive X-ray (EDX) studies

Energy Dispersive X-ray (EDX) spectra for present ferrite systems


were used to check the stoichiometry of samples. The characteristic
spectra are displayed in Fig. 3 and the results are summarized in
Fig. 2. XRD of Pure and Ag substituted Cobalt ferrite nanoparticles: (a) as- Table2. The calculations of elemental composition ratios of the samples
prepared cobalt ferrite, (b) 600 °C annealed cobalt ferrite, (c) as-prepared Ag- are consistent with the expected stoichiometry considered under pre-
cobalt ferrite (d) 600 °C annealed Ag-cobalt ferrite. paration. The atomic percentages of Ag in the Ag-doped CoFe2O4 con-
firm the presence of Ag-nanoparticles. However, a small difference of
Ag in the spinel structure. The size of silver nanoparticles in the pre- Ag is about 0.21% has been observed between the prepared and the
pared sample and in the annealed sample is estimated to be 46.8 nm annealed sample of Ag-doped CoFe2O4. This is probably due to the non-
and 62.7 nm. The crystallite sizes of the prepared and the annealed un- uniform distribution of Ag-nanoparticles in the cobalt ferrite network.

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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

Fig. 3. EDX spectra of Pure and Ag substituted cobalt ferrite nanoparticles: (a) as-prepared cobalt ferrite, (b) 600 °C annealed cobalt ferrite, (c) as-prepared Ag-cobalt
ferrite (d) 600 °C annealed Ag-cobalt ferrite.

Table 2 3.4. Magnetic studies


Elemental compositions of (1–x)CoFe2O4: xAg (x = 0.0, 0.2) - Sample A(as
burnt CoFe2O4), Sample B (annealed CoFe2O4), Sample C(as burnt Ag-CoFe2O4) Magnetic behaviour of the pure cobalt ferrite and the Ag doped
and Sample D (annealed Ag-CoFe2O4). cobalt ferrite nanoparticles at room temperature have been studied
Samples Co:Fe Fe:O Ag using vibrating sample magnetometer (VSM) and the respective mag-
netization curves are shown in Figs. 6 and 7. The saturation magneti-
Sample A 0.57 0.48 – zation (Ms), remnant magnetization (Mr), coercivity (Hc), and square-
Sample B 0.52 0.42 –
ness ratio (S = Mr/Ms) are listed in Table 1.The wide feature of
Sample C 0.5 0.47 1.15
Sample D 0.56 0.49 0.94 hysteresis loops indicates that all of the samples have hard magnetic
character. The magnetization in ferrites depends on both the magneti-
zations at octahedral (B) and tetrahedral (A) sites, and is given as
M = |MB MA|, where MB and MA are the magnetizations at A- and B-
sites. The cations’ distribution is the predominant factor for the mag-
3.3. SEM and TEM studies
netizations at A- and B- sites. The reported values Ms = 60 emu/g for
the annealed CoF2O4 is less than that of bulk CoF2O4 (Ms ∼ 87 emu/g)
Morphology of the undoped and the Ag doped CoFe2O4 nano-
[18]. This is attributed to the – cations’ redistribution in spinel structure
particles annealed at 600 °C were investigated using scanning electron
unlike the normal distribution. The process of downsizing the particles
microscopy (SEM), and corresponding micrograms are shown in Fig. 4.
to nanoscale dimensions leads to the decrease of surface energy. This is
The morphological changes in samples due to doping and annealing are
not enough to retain the actual distribution of cations in the spinel
clearly evident from the nature of SEM micrograms. The particle size
structure. Therefore, cations’ redistribution may be happening against
and shape of the as-burnt samples of the undoped and the Ag doped
to their normal preferences which will affect the magnetizations at A–
cobalt ferrite NPs have been recorded using transmission electron mi-
and B– sites. The saturation magnetization (Ms) values of the Ag sub-
croscopy (TEM). TEM images and histograms are presented in
stituted Co-ferrite were found to be lower than that of the corre-
Fig. 5.TEM images of the as-burnt sample (the undoped and the Ag
sponding Co-ferrite. The substitution of diamagnetic Ag for Co in the
doped) show that the shapes of the ferrite nanoparticles are nearly
spinel structure may substantially lower the magnetization of CoFe2O4.
spherical and polyhedron. The distribution of particles of different sizes
On the other perspective, in the ferrite sample with smaller crystallite
have been revealed from the histograms and the average particle sizes
sizes (See Table 1) has a probability of possessing higher non-collinear
for the as-burnt cobalt ferrite and the Ag doped cobalt ferrite are found
shell region than that of the ferrite core [19,20]. Increasing number of
to be 25.2 nm and 28.4 nm respectively. The agglomeration of Ag na-
un-coordinated magnetic spins on the surface of the shell layer which
noparticles on the ferrite nanoparticles may be resulted a bigger par-
are not able to align in the direction of external magnetic field may also
ticle size in the Ag doped CoFe2O4. Similar studies have been reported
be responsible for the decrease of saturation magnetization of the Ag
in the literature [17]. The average particle sizes estimated from histo-
doped CoFe2O4. Kooti et al. [21] reported the similar variation of Ms in
grams are consistent with the crystallite size Destimated from the XRD
Ag-coated CoFe2O4 nanoparticles, and they reported this is due to the
analysis. The superimposition of bright spots observed in the SAED
decrease in ferrite core and increase in shell consisting of AgNPs. The
pattern of the ferrite sample recorded through a transmission electron
acquired magnetization in the pure CoFe2O4 and the Ag doped CoFe2O4
microscope is an indicative of polycrystalline nature of ferrite samples
is increased with the heat treatment. This is attributed to the Oswald
[16] that is supporting the particle distribution as observed from XRD
ripening of particle sizes that depends on sintering process. From the
and TEM.

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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

Fig. 4. SEM micrograms of Pure and Ag substituted cobalt ferrite nanoparticles: (a) as-prepared cobalt ferrite, (b) 600 °C annealed cobalt ferrite, (c) as-prepared Ag-
cobalt ferrite (d) 600 °C annealed Ag-cobalt ferrite.

VSM results, it can be observed that the coercivity (Hc) is decreased in abundant aspects like magnetocrystalline anisotropy, microstrain, size
pure the CoFe2O4, but it is increased in the Ag doped CoFe2O4 with the distribution and magnetic domain size [22–24]. The variation of Hc in
heat treatment. The above oscillation of Hc may be influenced by the pure CoFe2O4 can be explained in the following way; in the multi

Fig. 5. TEM and HR-TEM images of as-prepared pure and Ag substituted cobalt ferrite nanoparticles.

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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

Fig. 6. Magnetic measurements of cobalt ferrite nanoparticles (a) as-prepared


and (b) annealed at 600 °C.

Fig. 8. Antimicrobial activity of CoFe2O4 and AgCoFe2O4 against (A) & (B)
Staphylococcus aureus, (C) & (D) Escherichia coli, (E) & (F)Candida albicans.

study, it can be observed that the width of the hysteresis loop is de-
creased with the substitution of Ag in the spinel structure of CoFe2O4.
This indicates that the nature of magnetization is transforming from the
ferromagnetic order to superparamagnetic order with the substitution
of Ag, resulting the decrease of magnetocrystalline anisotropy. The
decrease of magnetocrystalline anisotropy is the probable reason for the
low of Hc in the Ag doped CoFe2O4 when compared with the pure
CoFe2O4 in the present studies. The isotropic nature of present ferrite
samples is evident by noticing with low value of squareness ratio which
is in the range of 0.29 to 0.37.

3.5. Antibacterial activity studies


Fig. 7. Magnetic measurements of Ag substituted cobalt ferrite nanoparticles
(a) as-prepared and (b) annealed at 600 °C.
Antimicrobial property of the CoFe2O4 and the Ag doped CoFe2O4
were analyzed by treating two bacteria Staphylococcus aureus,
Escherichia coli and fungus Candida ablicans with varying concentrations
domain system, Hc is varied inversely to D and to Ms. Moreover, it was 100–500 mg. The viability was assessed by the determination of clear
observed that the Hc in the Ag doped CoFe2O4 is less than that of the zone of inhibition around the disc after 48-h incubation. The obtained
pure CoFe2O4. These results are quite contrast to the results reported by results are presented in Table 3, and the respective images inhibition
Kooti et al. [21]. Shukla et al. [25] also observed higher value of Hc in zones are shown in Fig. 8. It can be observed that as the concentration
the Ag doped CoFe2O4 than that of the pure CoFe2O4 and they reported of nano particles is increased, microbial cultures are decreased. Both
this is due to increase in magnetocrystalline anisotropy. In the present nano particles show good antimicrobial action against Staphylococcus

Table 3
Inhibitory activity of CoFe2O4 and AgCoFe2O4.
Sample Microbes Zone of inhibition in mm

100 200 300 400 500 Streptomycin (10 mg)

CoFe2O4 E.coli 7.5 ± 0.20 8.0 ± 0.7 8.5 ± 0.04 9.0 ± 0.8 9.5 ± 0.04 18.66 ± 0.47
S.aureus 9.0 ± 0.41 9.5 ± 0.01 8.5 ± 0.01 8.75 ± 0.20 10.0 ± 0.41 18.66 ± 0.47
C.albicans 8.0 ± 0.08 9.5 ± 0.62 10.05 ± 0.23 12.5 ± 0.01 15.0 ± 0.07 27.8 ± 0.16

AgCoFe2O4 E.coli 8.0 ± 0.08 8.5 ± 0.06 9.3 ± 0.23 10.5 ± 0.01 10.5 ± 0.08 18.66 ± 0.47
S.aureus 6.5 ± 0.06 6.8 ± 0.04 7.5 ± 0.01 7.86 ± 0.20 8.5 ± 0 19.03 ± 0.12
C.albicans 8.0 ± 0.04 8.5 ± 0.31 8.93 ± 0.09 16.13 ± 0.18 20.03 ± 0.47 29.17 ± 0.23

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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697

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