Materials Chemistry and Physics 120 (2010) 509517

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Materials Chemistry and Physics
j our nal homepage: www. el sevi er . com/ l ocat e/ mat chemphys
Wet chemical synthesis and gas sensing properties of magnesium zinc ferrite
nano-particles
D.C. Bharti, K. Mukherjee, S.B. Majumder

Materials Science Center, Indian Institute of Technology, Kharagpur 721302, West Bengal, India
a r t i c l e i n f o
Article history:
Received 22 June 2009
Received in revised form
25 November 2009
Accepted 28 November 2009
Keywords:
Semiconducting oxide
Solgel growth
X-ray diffraction
Adsorption
a b s t r a c t
Inthepresent workwehavesynthesized, magnesiumferrite, zinc ferrite, andmagnesiumzinc ferritesolid
solutions usinganeconomic wet chemical synthesis route. Tounderstandthephaseformationbehavior of
the synthesized powders, infra-red spectroscopy in conjunction with X-ray Rietveld renement analyses
has been performed. The structural characteristics of these ferrite powders are correlated with their
roomtemperature magnetic properties. Phase pure, lowtemperature synthesizedmagnesiumzinc ferrite
nano-particles are investigated in terms of carbon monoxide and hydrogen gas sensing properties. The
response and recovery transients of conductance are modeled using Langmuir adsorption kinetics with
two active sites in the sensing elements used as CO sensors. For these two adsorption sites the activation
energies for response and recovery behavior, estimated from the temperature dependence of respective
time constants are found to be different. The difference in respective activation energies for response as
well as recovery is thought to be due to different chemi-adsorbed oxygen species in these two sites.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Cubic spinel ferrites are one of the most attractive materials for
magnetic, catalysis, micro-electronic, as well as gas sensing appli-
cations [15]. The magnetic cations in cubic spinel lattice occupy A
(divalent, tetrahedrally coordinated with oxygen) and B (trivalent,
octahedrally coordinated with oxygen) types of crystallographic
positions. In this type of materials, ferrimagnetisms may result
fromstronger ABantiferromagnetic interactionthanthe BBanti-
ferromagnetic interaction. Magnesium ferrite (MgFe
2
O
4
(MFO)),
zinc ferrite (ZnFe
2
O
4
(ZFO)) and the solid solutions between these
two crystallize into cubic spinel structure and have several impor-
tant technological applications. The cation distribution in MFO is
predominantly inverse whereas ZFO crystallizes in normal spinel
structure. The reported magnetic properties of these materials are
scattered and strongly depend on their synthesis routes. As for
example, for MFO powders prepared by high energy ball mill, sec-
ondary phase formation(e.g. MgO, Fe
2
O
3
) as well as cationmixing
(inverse or mixed) is reported to be related to the milling time
[6]. In mechano-chemical synthesis too the co-existence of Fe
2
O
3
with MFO is related to milling time [7]. MFO prepared using dou-
ble hydroxide precursor have secondary MgOco-existed with MFO
[8]. Efforts have been made to correlate magnetic properties with
secondary phase contents; microstructure and compositional het-
erogeneity.

Corresponding author. Tel.: +91 3222 283986.

E-mail address: subhasish@matsc.iitkgp.ernet.in (S.B. Majumder).
From several recent literatures it is apparent that in nano-
crystalline form, the properties of these ferrite materials are very
different fromtheir bulk counterpart. As for example, belowa criti-
cal particlesizeMFOexhibits super-paramagnetic behavior at room
temperature [9]. Since Mg
2+
is diamagnetic, a weaker coupling
between Fe
3+
cations reduces the anisotropic energy in MFOwhich
also yield super-paramagnetismat roomtemperature. These ultra-
ne super-paramagnetic particles may have several applications
viz. as magnetic resonance imaging contrast agents, in ferro-uid
based technology, also in high density information storage device,
etc. Nano-crystalline ferrite particles have also reported to exhibit
superior gas sensing properties than their bulk counterpart [10].
Interestingly, some of these ferrite particles also exhibit distinct
selectivity for a specic gas in a gas mixture [11].
In the present work we have synthesized (Mg
1x
Zn
x
)Fe
2
O
4
(0.0x 1.0) solid solution particles using a simple, economic wet
chemical synthesis route. These powders are calcined in a temper-
ature range between 300 and 900

C. The phase formation behavior

of MgFe
2
O
4
, ZnFe
2
O
4
and (Mg
1x
Zn
x
)Fe
2
O
4
solid solution pow-
ders calcined at different temperatures are studied systematically
using Rietveld renement of the X-ray diffractograms. The mor-
phology as well as room temperature magnetic properties of these
calcined powders are characterized using transmission electron
microscope (TEM) and a vibrating sample magnetometer vibrating
sample magnetometer (VSM).
We have also investigated the hydrogen and carbon monoxide
sensing performance of the low temperature synthesized phase
pure (Mg
0.5
Zn
0.5
)Fe
2
O
4
particles. The synthesized particles are
lightly pressed and sintered at lowtemperature in order to achieve
0254-0584/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2009.11.050
510 D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
a microstructure that contains both macro-pores and meso-pores
to yield molecular as well as Knudsen gas diffusion behavior [12].
The gas sensing performance of the ferrite is evaluated in a spe-
cially designed home made dynamic gas sensing measurement
system. The kinetics of the response as well as recovery behav-
ior is investigated through the analyses of respective conductance
transients which are found to t reasonably well assuming Lang-
muir adsorption kinetics model [13]. The variation of relaxation
times during response and recovery as a function of gas con-
centration and temperature has been studied and the underlying
mechanism/(s) controlling the carbon monoxide sensing behavior
of Mg
0.5
Zn
0.5
Fe
2
O
4
is discussed.
2. Experimental
Nano-crystalline magnesium zinc ferrite powders are prepared using a wet
chemical synthesis route using hydrated magnesiumacetate (Mg(CH
3
COO)
2
2H
2
O),
hydratedzinc acetate (Zn(CH
3
COO)
2
2H
2
O) andironnitrate (Fe(NO
3
)
3
9H
2
O) as pre-
cursor materials. For the powder synthesis, stoichiometric precursor materials of
Mg, Zn and Fe cations are dissolved in hot acetic acid through continuous stirring.
Poly-vinyl alcohol (PVA) solution (2%) is added into the mixed precursor solution
(in 1:0.25 volume ratio) and the resultant precursor is repeatedly heated 80

C and
cooled in an ice bath to yield a gelled mass. The gel is dried in a vacuum oven kept
about 80

C overnight to form powder. The resultant powder, termed as dried pow-

der, is crushed ina mortar pestle and calcined ina two step heat treatment schedule.
In the rst step, the powders are red at 400

C for 1h for the removal associated

organics followed by a second step calcination in a temperature range between 600
and 900

C for 2h. The powders prepared below 400

C are calcined in a one step

heat treatment process in respective temperature for 2h for crystallization.
The phase formation behavior of the calcined powders are studied using Fourier
transformed infra-red (FTIR) spectroscopy and X-ray diffraction analyses. A trans-
mission electron microscope (TEM) is used to study the microstructure evolution.
The roomtemperature measured magnetic properties of the synthesized powder is
characterized using a VSM. The synthesized powders are mixed with few drops of
10% PVA solution as binder and pressed in the form of thin circular discs (12mm
diameter 0.1mm thick) using a hydraulic press. The pellets are heated at 600

C
for 2h in air. The above heat treatment ensures minimal particle growth, necking
betweenparticles, sufcient handling strengthandporous nature of the sensing ele-
ment. The sintered pellets are polished on a velvet cloth and cleaned ultrasonically
for 2min each in acetone followed by water and absolute alcohol. For the electrical
measurements, one of the surfaces of the sensing elements are sputter coated with
planar gold stripes of 7mm length, 3mm wide and separated from each other by
4mm. The sensing element is placed in a reactor equipped with pressure contact
probes and heater assembly with precise temperature control. For gas sensing stud-
ies hydrogen and carbon monoxide gas diluted in N2
(10,000ppm) and compressed
air (95%+ purity) is used as test and carrier gas, respectively. The ow rates of test
(dVtest/dt) as well as carrier gas (dV
carrier
/dt) are controlled by mass ow controllers
interfaced with a PC. Both test and carrier gas with controlled ow rate is fed to
the reactor through a home made mixing unit. During the sensing measurements
continuous ow of test as well as carrier gas is maintained through the reactor to
the exhaust line of it. The concentration of the mixed gas (C
mixedgas
) in the reactor is
calculated using the following relation:
C
mixedgas
=
Ctest gas (dVtest/dt)
(dVtest/dt) +(dV
carrier
/dt)
(1)
The probes are connected to an electrometer (6517A, Keithley Instruments)
which acts as a source-measure unit for resistance measurements. The mass ow
controllers (MFC) (PR 4000, MKS Technology and Products), electrometer and tem-
perature controller (6400 West Instruments.) are all interfaced with a PC equipped
with a general purpose interface bus (GPIB) card (National Instruments) and Lab-
view 8.5 (National Instruments) software. For the resistance measurements a xed
voltage of 1V is applied to one of the planar electrodes and the surface current is
measured. In the voltage range between 1 and 5V an Ohmic behavior is observed
and from the measured current, resistance is calculated. To evaluate the sensing
characteristics of (Mg,Zn)Fe2
O
4
, its planar resistance is measured as a function of
time varying either the gas concentration at constant temperature or varying the
temperature keeping the gas concentration constant. From the measured value of
equilibriumresistance inair (Ra) andgas (Rg), the sensitivity (S) was calculatedusing
the relation
S =
_
Ra Rg
Ra
_
100 (2)
3. Results and discussion
3.1. Structural analyses of (Mg
1x
Zn
x
) Fe
2
O
4
(0.0x 1.0)
(MZFO) powders
Fig. 1shows the X-raydiffractograms of (a) x =0.0, (b) x =0.25, (c)
x =0.50, and (d) x =0.75 and (e) x =1.0 as dried and calcined MZFO
powders in the temperature range of 300900

C for 2h in air. Note

that for all these compositions, powders calcined at temperature
as low as 300

C, crystallize into cubic spinel structure. At lower

calcination temperature, minute quantity of unreacted MgO and
ZnO phase co-exist in Mg and Zn rich composition, respectively. At
higher calcination temperature (600

C) in some cases (especially

in Mg rich compositions) Fe
2
O
3
co-exists as impurity phase. It
is interesting to note that phase pure Mg
0.5
Zn
0.5
Fe
2
O
4
crystallizes
at 300

C (Fig. 1(c)). Comparing the FWHM of the XRD pattern of

Mg
0.5
Zn
0.5
Fe
2
O
4
calcined at different temperatures it is apparent
that powder calcined at 300

C may have ultra-ne crystallite size.

The space group of spinel ferrite is Fd3m. The cations are located
in tetrahedral and octahedral voids. The two most prominent infra-
red vibration modes (
1
and
2
, respectively) for MgFe
2
O
4
(MFO)
are reported to be at 565 and 406cm
1
and for ZnFe
2
O
4
(ZFO)
are 555 and 393cm
1
, respectively [14]. From the detailed lattice
dynamics analyses it has been suggested that the tetrahedral bond
have the effect of substantially increasing the frequency for vibra-
tion along (tetrahedral) cation oxygen (C
T
O) axis. This would lead
to the IR absorption mode at
1
. The other absorption at relatively
lower frequency(
2
<
1
) is associatedwiththevibrationof oxygen
ions in the direction perpendicular to the C
T
O axis. The potential
energy (V) of the system is dened as
2V = K
t

r
2
t
+K
0

r
2
0
(3)
where K
t
and K
o
are the force constants associated with unit dis-
placement of the C
T
O and C
o
O bonds, and r
t
and r
0
represents
the corresponding components of displacement from equilibrium
inthe directionof the appropriate bond. Fromthe measured
1
and

2
frequencies the force constants for the tetrahedral and octahe-
dral cations can be determined [15]. If more than one type of cation
is present in the respective sites, the effective mass (summation
of the product of respective masses and their weight fraction) will
inuence the force constant which eventually leads to the shift of
the tetrahedral and octahedral frequencies. Therefore, the shift of
the frequencies is related to the cation distribution in the tetrahe-
dral and octahedral sites. Finally, depending on the distribution of
the cations the cationoxygen bond lengths in the tetrahedral and
octahedral sites will be changed.
We have recorded the FTIR spectra of as prepared as well as cal-
cinedMFOandZFOpowders at different temperatures (not shown).
Two important features are apparent from these gures, rst: the
mode frequencies for tetrahedral cation/(s) are invariant to the cal-
cination temperature and second the width of the absorption mode
decreases with the increase in calcination temperature. The atomic
weight of Mg, Zn, and Fe are 24.31, 65.37, and 55.84. Therefore, any
change of their fractional contents in A (tetrahedral) or B (octa-
hedral) sites would change the values of
1
and
2
appreciably.
However, both for MFO and ZFO it is observed that the mode fre-
quencies for tetrahedral sites (
1
) are invariant to the calcination
temperature; therefore, it seems that the cation distribution does
not alter withcalcinationtemperature inbothpowders. The second
observation indicates that the crystallinity of MFO/ZFO powders
improves with the increase in calcination temperature. Similar to
that for the end members MFO and ZFO, for all their solid solution
compositions, we have observed that the mode frequency due to
tetrahedral bond does not shift appreciably with calcination tem-
perature. As observed also in case of the end members MFO and
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517 511
Fig. 1. X-ray diffractograms of Mg
1x
ZnxFe
2.0
O
4
(0.0x 1.0) powders calcined in the temperature range of 300900

C for 2h in air.
ZFO, this indicates that cation occupancy in tetrahedral and octa-
hedral site is invariant to the calcination temperature. However,
interesting variation of the mode frequency is observed when we
compare FTIR spectra of the solid solutions calcined at identical
temperatures. Thus, Fig. 2 shows the FTIR spectra of MZFO pow-
ders calcined at 900

C. Note that as the Zn contents in the solid

solution are increased the tetrahedral mode frequency is shifted
to lower wave number. This is expected as Zn has higher atomic
mass as compared to Mg ion in a specic crystallographic lattice
site.
In order to quantify structural and microstructural parameters,
we have performedRietveldrenement of the X-raydiffractograms
of the MZFO powders. The Rietveld renement is done for all the
MZFO powders calcined at 300900

C and a typical renement

plot is shown in Fig. 3 for MZFO powder calcined at 300

C for 2h.
The rened composition, structural and microstructural parame-
ters (i.e. phase, volume fraction, lattice parameter, rms microstrain,
and crystallite size) as well as the statistical tting parameters for
MFO, MZFO (50:50) and ZFO powders calcined at 300

C for 2h
is tabulated in Tables 13, respectively. The continuous range of
512 D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
Table 1
Rened structural and microstructural parameters of magnesium Ferrite powders
calcined at 300

C for 2h.
Magnesium ferrite MgFe
2
O
4
(MFO) Rened composition
Phase/(s) present (SG) (Mg
0.14
Fe
0.86
)T(Mg
0.86
Fe
1.14
)
O
O
4
MFO cubic spinel (Fd-3m) 82wt% Statistical parameters
MgO cubic (Fm-3m) 18wt% RWp 5.6%
Calcination temperature 300

C RP 4.87%
Rened parameters (MFO) R
wbp
4.47%
Lattice parameter () 8.38 (0.0014) R
pb
4.23%
Rms microstrain 0.0017%
Crystallite size (nm) 81.7 (2.09)
Density (gmcm
3
) 4.49 gmcm
3
Rened parameters (MgO)
Lattice parameter () 4.23 (0.0011)
Crystallite size (nm) 145 (9.9)
Atom x y z (
2
)
MgT 0.125 0.125 0.125 1.21
FeT 0.125 0.125 0.125 1.21
Mg
O
0.5 0.5 0.5 0.37
Fe
O
0.5 0.5 0.5 0.37
O 0.255 0.255 0.255 0.713
the solid solution is conrmed by systematic change in the lattice
parameter as a function of Zn contents in MFO lattice. Fig. 4 shows
the variation of the lattice parameter of MZFO powders calcined
at 300 and 900

C. As shown in the gure, the lattice parameter is

increasedwiththe increase incalcinationtemperature as well as Zn
contents in MFO lattice. Similar to the end members MFO and ZFO,
the crystallite size of MZFOsolidsolutionwas foundto be increased
withthe increase incalcinationtemperature. For Mg
0.5
Zn
0.5
Fe
2.0
O
4
(MZFO50:50) compositioncalcinedat 300and900

Cthecrystallite
size was foundto be 11.1and151nm, respectively. The particle size
of MZFO 50:50 powders calcined at 300 and 900

C was also inves-

tigated using a transmission electron microscope (not shown). It is
interesting to note that the particles are spherical and their average
size matches quite well with the X-ray derived crystallite size only
in case of powder calcined at elevated temperature. The crystal-
lite size corresponds to the regions of coherent X-ray diffraction
and these regions are single crystalline in nature. In the parti-
cles calcined at lower temperature (300

C), the crystallite size

as determined by XRD is smaller in size (11nm). These crystal-
lites (termed as primary particle) are aggregated to form relatively
bigger particles (termedas secondaryparticles). Thesecondarypar-
ticles are not single crystalline in nature and the particle size as
determined by TEM studies (corresponding to the secondary par-
ticles) are therefore bigger than that has been estimated from the
X-ray diffractograms. When these particles are calcined at higher
Table 3
Renedstructural andmicrostructural parameters of ZFOpowders calcinedat 300

C
for 2h.
Zinc ferrite ZnFe
2
O
4
(ZFO) Rened composition
Phase/(s) present (SG) (Zn
0.92
Fe
0.08
)T(Zn
0.08
Fe
1.92
)
O
O
4
ZFO cubic spinel (Fd-3m) 93wt% Statistical parameters
ZnO cubic (P63mc) 7wt% RWp 6.93%
Calcination temperature 300

C RP 5.15%
Rened parameters (ZFO) R
wbp
8.55%
Lattice parameter () 8.43 (0.0014) R
pb
6.54%
Rms microstrain 0.0085%
Crystallite size (nm) 38.0 (0.69)
Density (gmcm
3
) 5.37gmcm
3
Rened parameters (ZnO)
Lattice parameter () a =3.25 (0.0011), c =5.20
Crystallite size (nm) 100 (9.9)
Atomic coordinates
Atom x y z (
2
)
ZnT 0.125 0.125 0.125 0.68
FeT 0.125 0.125 0.125 0.68
Zn
O
0.5 0.5 0.5 0.68
Fe
O
0.5 0.5 0.5 0.68
O 0.255 0.255 0.255 0.67
temperature the individual crystallites in the secondary particles
grow and each individual particle becomes single crystalline to
yield coherent X-ray diffraction. Therefore, the particle calcined at
higher temperature the crystallite size matches quite well with the
particle size estimated by TEM measurements.
3.2. Magnetic properties of MZFO calcined powder
We have measured the room temperature hysteresis loops of
MgFe
2
O
4
(MFO) powders calcinedat 300and900

Cfor 2h. For both

the cases a well saturated magnetic hysteresis loops are obtained.
For powders calcined at 300 and 900

C the remnant, saturation

magnetization and coercive eld values are 7.01, 38.45emug
1
and 84.5Oe and 5.22, 22.76emug
1
, 80.52Oe, respectively. The
saturation magnetization of the MFO powder calcined at lower
temperature (300

C) is close to that reported in bulk MgFe

2
O
4
(30emug
1
) by others in the literature [16]. The reduction in the
magnetization values of MFO powder calcined at higher temper-
ature (900

C) is thought to be due to the presence of Fe

2
O
3
impurity phase as emerged in X-ray diffractograms presented
earlier (Fig. 1(a)). It is interesting to note that the measured sat-
uration magnetization is very close to the calculated magnetic
moment (33emug
1
) assuming the mixed spinel rened com-
Table 2
Rened structural and microstructural parameters of MZFO (50:50) calcined at 300

C for 2h.
Magnesium zinc ferrite (Mg
0.5
Zn
0.5
)Fe
2
O
4
Statistical parameters
Phase/(s) present (SG) RW 5.04%
Cubic spinel (Fd-3m) 100wt% R
wnb
4.81%
Calcination temperature 300

C R 4.05%
Rened parameters R
nb
4.23%
Lattice parameter () 8.42 (0.0064) Rened composition
Rms microstrain 0.0007% (Mg
0.04
Zn
0.46
Fe
0.50
)T(Mg
0.46
Zn
0.04
Fe
1.50
)
O
O
4
Crystallite size (nm) 11.1 (0.143)
Density (gmcm
3
) 4.89gmcm
3
Atom x y z (
2
)
MgT 0.125 0.125 0.125 1.28
ZnT 0.125 0.125 0.125 1.28
FeT 0.125 0.125 0.125 1.28
Mg
O
0.5 0.5 0.5 1.12
Zn
O
0.5 0.5 0.5 1.12
Fe
O
0.5 0.5 0.5 1.12
O 0.2555 0.2555 0.2555 1.21
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517 513
Fig. 2. FTIR spectra of Mg
1x
ZnxFe
2.0
O
4
(0.0x 1.0) powders calcined at 900

C for
2h in air.
position (Mg
0.14
Fe
0.86
) (Mg
0.86
Fe
1.14
) and density (4.49gcm
3
) as
presented in Table 1. As emerged through the Rietveld structural
renement studies presented above, ZnFe
2
O
4
powders crystallize
into a mixed spinel structure with a very low degree of cation
mixing ( 0.08). In that respect, ZFO can be considered to have
a normal spinel structure. ZFO powder exhibits a typical param-
agnetic behavior similar to that reported in the literature [17].
Fig. 5 shows the room temperature hysteresis loops of MZFO
50:50 powders calcined at 300 and 900

C for 2h in air. As envis-

aged from the hysteresis loop, both the powders calcined at 300
and 900

C, exhibit S type hysteresis loops and the magnetiza-

tion increases with the increase in calcination temperature. As
mentioned earlier, ZFO exhibits typical paramagnetic ordering at
room temperature. In magnesium zinc ferrite replacing part of Mg
cation by Zn would reduce the strength of the exchange interaction
between the tetrahedral (A) and octahedral (B) cations. This may
induce the super-paramagnetic behavior in MZFO solid solutions.
Although in several recent literature report super-paramagnetic
behavior has been concluded merely from room temperature hys-
teresis loopmeasurements [15], ideally one shouldget it conrmed
from the zero eld cooled and eld cooled magnetization mea-
surement. In zero eld cooled measurement, the system is cooled
fast in zero magnetic elds. Then the magnetization is measured as
temperature T is increased. A eld cooled magnetization curve is
obtained by measuring magnetization at step wise decreasing tem-
perature applying a weak magnetic eld. In super-paramagnetic
Fig. 3. X-ray Rietveld renement plot of Mg
0.5
Zn
0.5
Fe
2.0
O
4
powders calcined at
300

C for 2h in air.
materials the zero eld cooled magnetization curve deviates from
the eld cooled magnetization curve at a characteristic blocking
temperature (T
B
). Below the blocking temperature one observes
magnetic hysteresis in super-paramagnetic materials. In line to
this, further temperature dependent magnetizationmeasurements
are required to conrm the super-paramagnetic behavior in the
measured composition as well as in other solid solution composi-
tions.
3.3. Gas sensing performance of porous (Mg
0.5
Zn
0.5
)Fe
2
O
4
pellet
As envisaged from the Rietveld structural renement analyses,
only the (Mg
0.5
Zn
0.5
)Fe
2
O
4
powders calcined at 300

C are phase
pure and crystallized in cubic spinel structure. These powders are
pressed in the form of circular pellet, sintered at 600

C for 2h and
studied in terms of their H
2
and CO sensing properties. In the pres-
ence of hydrogen gas in the concentration range of 1001660ppm,
the resistance transient of Mg
0.5
Zn
0.5
Fe
2
O
4
porous pellet (mea-
sured at an operating temperature 380

C) is shown in Fig. 6. The

gas on and off state at each of this gas concentration is denoted
by down and up arrow, respectively. When the gas ow is turned
off, the sensor recovery is achieved by owing 500ppm air into
the measurement unit. Minimal base-line drift is observed when
Fig. 4. Variation of the lattice parameter of Mg
1x
ZnxFe
2.0
O
4
(0.0x 1.0) powders
calcined at 300 and 900

C for 2h in air.
514 D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
Fig. 5. Room temperature magnetic hysteresis loops of Mg
0.5
Zn
0.5
Fe
2.0
O
4
powders
calcined at 300 and 900

C for 2h in air.
the sensing element is switched back and forth between air and
test gas environment. The sensitivity is found to increase from
10% to 62% when the H
2
concentration was increased from100 to
1660ppm. For a xed gas concentration (H
2
/CO1660ppm), Fig. 7
shows the temperature dependent sensitivity of Mg
0.5
Zn
0.5
Fe
2
O
4
sensors. As shown in the gure, in case of CO sensing a maxi-
mumsensitivity(44%) is achievedat operatingtemperature about
320

C. However, incase of H
2
sensing the sensitivityincreases with
the operating temperature of the sensing element. The slope of S
vs. T, however, starts to decrease 350

C and as envisaged from

the gure, probably the sensitivity (S) would have a tendency to
decline beyond 380

C. Due to the limitation of the heating unit

we could not measure the sensitivity beyond 380

C. Several physi-
cal phenomena could be invoked to explain the observed behavior.
For example, such reduction of sensitivity at higher temperature
may be explained by the adsorptiondesorption principle. Thus the
enhancement of desorption rates at the sensor surface may lead to
the decreased sensitivity at higher temperature. Additionally, the
Fig. 6. The resistance transient of Mg
0.5
Zn
0.5
Fe
2
O
4
porous pellet in the presence
of different concentration of hydrogen gas, measured at an operating temperature
380

C.
behavior can also be explained using the depleted layer width (L
D
)
concept. For the semiconducting material the charge carrier con-
centration (n
0
) (and therefore the conductance) increases with the
increase in temperature. The relation between the depletion layer
width (L
D
) with carrier concentration (n
0
) and response (S) is given
in Eqs. (4) and (5), respectively [18]
L
D
=
_

0
kT
n
0
e
2
_1/2
(4)
S =
n
n
0
L
D
(5)
where
0
is the static dielectric constant, n
0
is the total car-
rier concentration, e is the carrier charge, k is the Boltzmann
constant, T is the absolute temperature, n is the change in
the carrier concentration. From these equations it is clear that
beyond a critical temperature, the sensitivity is reduced due to the
decrease in depletion layer width. Table 4 compares the H
2
and
CO sensing characteristics of various cubic spinel ferrite reported
in recent literatures. Comparing these data, it is ascertained that
Mg
0.5
Zn
0.5
Fe
2
O
4
prepared by a simple economical wet chemical
synthesis route exhibit reasonably good CO and H
2
sensing behav-
ior.
The sensing mechanism for the reducing gases such as H
2
(or
CO) involves the formation of electron accepting adsorbates on the
surface of ceramic oxides as described in several recent research
Fig. 7. Temperature dependent H
2
and CO sensitivity of Mg
0.5
Zn
0.5
Fe
2
O
4
sensor.
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517 515
Table 4
H
2
and CO sensing characteristics of various cubic spinel ferrites.
Composition Synthesis route Morphology Measurement system Sensor characteristics Ref.
Topt (

C) S H
2
(ppm) CO (ppm)
ZnFe
2
O
4
Molten salt Thick lm Dynamic 250 45 200 [19]
CuFe
2
O
4
Solid state reaction Powder Static 332 20 1000 [20]
CuFe
2
O
4
[21]
ZnFe
2
O
4
Chemical route Thick lm Dynamic 250400 40 (H
2
) NA
CoFe
2
O
4
40(CO) NA
NiFe
2
O
4
CuFe
2
O
4
[22]
ZnFe
2
O
4
Chemical route Thick lm Static 250400 40 (H
2
) 6000
CdFe
2
O
4
40 (CO) 6000
MgFe
2
O
4
NiFe
2
O
4
Chemical route Pellet Dynamic 400 20 (H
2
) 200 [23]
BiFe
0.6
Mn
0.4
O
3
Solgel method Thick lm Static 300 22 (CO) 1000 [24]
CdFe
2
O
4
Coprecipitation Thick lm Static 350 25 (H
2
) 1000 [25]
25 (CO) 1000
Mg
0.5
Zn
0.5
Fe
2
O
4
Wet chemical synthesis Porous pellet Dynamic 380 62 (H
2
) 1660 This work
320 44 (CO) 1660
Table 5
Fitted parameters for the response kinetics as a function of temperature at xed (1660ppm) CO gas concentration.
Temperature (

C)
response
1
(s)
response
2
(s) G
0
(mho) G
1
(mho) G
2
(mho)
250 267.25 270.25 8.44e9 2.80e9 2.86e9
300 193.57 207.05 2.59e8 1.12e8 1.31e8
350 102.46 142.24 8.60e8 2.72e8 2.73e8
380 77.54 93.05 1.49e7 2.43e8 2.57e8
reports [26,27]. The rate of the increase of conductance (inresponse
transients) is in fact proportional to the steady state adsorbate
(gas molecules) concentration on the sensor surface. The rate of
adsorbate concentration () could be estimated fromthe following
equation of rst order kinetics [9]
d
dt
= K
a
(1 )[C
gas
] K
d
[] (6)
where K
a
and K
d
are the adsorption and desorption rate constants
and C
gas
is the concentration of the adsorbate gas. The steady state
adsorbate coverage [] of the gas molecule, which is proportional
to the conductance (G) can be estimated by the following relation
=
_
K
a
C
gas
K
a
C
gas
+K
d
_
[1 exp((K
a
C
gas
+K
d
) t)] (7)
For single adsorption site the conductance has the following
form
G(t)
response
= G
0
+G
1
_
1 exp
_

1
__
(8)
where G=G
0
, when t =0, G
1
is a constant and
1
=(K
a
C
gas
+K
d
)
1
is
the response time.
For recovery kinetics, C
gas
=0 and from Eq. (6) one can write
d
dt
= K
d
(9)
integrating Eq. (9) with the boundary condition at t =0, =1 one
gets
=
0
exp(K
d
t) (10)
Accordingly, the conductance recovery is given by
G(t)
recovery
= G

0
+G

1
exp
_

recovery
1
_
(11)
Attempts are made to t the (response) conductance transients
with a single site Langmuir isotherm (Eq. (8)). The ts were poor
with typical R
2
0.70. On the other hand the curve ts well with R
2
value >0.95 when two adsorption sites were assumed with modi-
ed G(t)
response
given by the following equation
G(t)
response
= G
0
+G
1
_
1 exp
_

response
1
__
+G
2
_
1 exp
_

response
2
__
(12)
where
response
1
and
response
2
are the relaxation times for two differ-
ent energetically different adsorption sites 1 and 2, respectively.
Similar to response the recovery is also found to t well assum-
ing two energetically different adsorption sites using the following
equation
G(t)
recovery
= G

0
+G

1
exp
_

recovery
1
_
+G

2
exp
_

2
recovery
_
(13)
Fig. 8 shows the conductance transient of Mg
0.5
Zn
0.5
Fe
2
O
4
used
as CO gas sensor at 500ppm (measured at T 300

C) and best
tted curve using Eq. (12) for response and Eq. (13) for recov-
ery. Similar tting is also performed for the response and recovery
transients of Mg
0.5
Zn
0.5
Fe
2
O
4
sensors measured at other operating
Table 6
Fitted parameters for the recovery kinetics as a function of temperature at xed (1660ppm) CO gas concentration.
Temperature (

C)
recovery
1
(s)
recovery
2
(s) G
0
(mho) G
1
(mho) G
2
(mho)
250 124.92 124.92 9.26e9 2.17e9 2.18e9
300 115.69 120.68 2.66e8 1.35e8 1.33e8
350 103.25 112.14 8.76e8 2.43e8 2.68e8
380 94.35 105.65 1.66e7 1.82e8 1.88e8
516 D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517
Fig. 8. Conductance transient for response and recovery of Mg
0.5
Zn
0.5
Fe
2
O
4
sensors
for 500ppm carbon monoxide measured at 300

C. The solid lines are calculated

using Eq. (12) (for response) and Eq. (13) (for recovery) (see text).
temperatures. The tted parameters of the conductance transient
of response as well as recovery for CO 1660ppm measured at
different operating temperatures are tabulated in Tables 5 and 6,
respectively. When the kinetics of sensor response is controlled
by adsorption/desorption process the response time constant ()
usually follow the following temperature dependence [28]
=
0
exp
_
E
A
+Q
2kT
_
(14)
where E
A
+Q is the activation energies for the adsorption of COgas.
Fig. 9 shows the plots of ln
response
1
andln
response
2
as a function
of 1000/T. From the slopes of these curves, activation energies for
adsorptionprocess at site 1and2were foundtobe 0.57and0.46eV,
respectively. As expected the two different adsorption sites have
different activation energies for CO adsorption. The recovery time
constants for site 1 and 2
recovery
1
,
recovery
2
are assumed to follow
following relation
=
0
exp
_
E
D
2kT
_
(15)
whereE
D
is the desorptionenergyfor ROgas. Accordingly, as shown
in Fig. 10 ln varies linearly with 1000/T and fromthe linear t the
activation energies of desorption for site 1 and 2 were estimated to
be 0.13 and 0.07eV, respectively.
Fig. 9. Plots of ln
response
1
andln
response
2
as a function of 1000/T for Mg
0.5
Zn
0.5
Fe
2
O
4
gas sensor in presence of 1660ppm CO gas.
Fig. 10. Plots of ln
recovery
1
andln
recovery
2
as a function of 1000/T for Mg
0.5
Zn
0.5
Fe
2
O
4
gas sensor in presence of 1660ppm CO gas.
Inlight of the above analyses, we are making anattempt to com-
ment on the nature of site 1 and site 2 as the different adsorption
sites in the magnesium zinc ferrite sensing elements. Note that as
compared to site 2, site 1 always exhibits faster response as well
as recoverykinetics (
response
1
,
recovery
1
<
response
2
,
recovery
2
). This in
turn indicates faster CO adsorption and CO
2
molecule desorption
from site 1 as compared to that from site 2. Probably, the sensor
block has macro-porous region (between secondary particles) and
meso-porous regions (between primary particles i.e. crystallites)
[29], then gas diffusion in macro-porous region (molecular) will be
faster (lower ) as comparedto that inmeso-porous regions (Knud-
sen diffusion). Finally, the difference in the respective activation
energies for site 1 and 2 (as derived from response and recovery
kinetics) probably indicates different types of oxygen are chemi-
adsorbed in these two sites. Further research is required to clarify
these issues.
4. Conclusions
In the present work we have synthesized multifunctional mag-
nesium ferrite, zinc ferrite and magnesium zinc ferrite solid
solution nano-powders using chemical solution synthesis route.
Through FTIR analyses in conjunction with XRDRietveld rene-
ment it is found that at a temperature as low as 300

C, MgFe
2
O
4
crystallizes into a mixed spinel structure with the degree of inver-
sion () 0.89. The degree of inversion is invariant to calcination
temperature. However, it is difcult to obtain phase pure MgFe
2
O
4
powders. The MgFe
2
O
4
powder calcined at a temperature as low
as 300

C exhibits ferrimagnetic behavior with remnant and sat-

uration magnetization 7.01 and 38.45emug
1
, respectively. Zinc
ferrite alsocrystallizedintoa mixedspinel structure, however, with
the degree of inversion () only 0.16 it can be considered as a
normal spinel. Similar to that of magnesium ferrite, the degree of
inversion is also found to be invariant to calcination temperature.
The measurement of magnetization vs. magnetic eld supports
paramagnetic ordering of zinc ferrite at room temperature. From
the FTIR analyses it is observed that the tetrahedral mode fre-
quency is shifted to lower wave number with the increase of Zn
contents in Mg
0.5
Zn
0.5
Fe
2
O
4
solid solutions. This is expected as Zn
has higher atomic mass as compared to Mg ion in a specic crystal-
lographic lattice site. The continuous range of the solid solution is
conrmed by systematic change in the lattice parameter as a func-
tion of Zn contents in MFO lattice. The Mg
0.5
Zn
0.5
Fe
2
O
4
powder
yields saturation magnetization 26emug
1
.
D.C. Bharti et al. / Materials Chemistry and Physics 120 (2010) 509517 517
The gas sensing performance of magnesium zinc ferrite is stud-
ied varying the carbon monoxide and hydrogen concentration in
the test gas (1001660ppm) for various operating temperature (in
the range of 250380

C) of the sensing elements. It is argued that

for magnesium zinc ferrite sensors the chemi-adsorption of the
reducinggas anddesorptionof thereactionproduct (carbondioxide
or water molecules) are the rate limitingprocesses for response and
recovery mechanisms, respectively. Through the analyses of con-
ductancetransients it is demonstratedthat for thesensingof carbon
monoxide gas, both the sensor response and recovery behavior can
be modeled assuming a two site Langmuir adsorption kinetics. It
is found that for both the adsorption sites, at constant temper-
ature T, Langmuir adsorption isotherm behavior is obeyed. For a
xed carbon monoxide concentration from the linear variance of
ln
response
vs. 1/T, the activation energies for the carbon monoxide
gas adsorption at two different adsorption sites are estimated to
be 0.57eV (for site 1) and 0.46eV (for site 2). Similar to response
kinetics ln
recovery
also follows a linear relationship with 1/T. The
activation energies for the desorption from site 1 and 2 are esti-
mated to be 0.13 and 0.07eV, respectively. Both for response and
recovery, the time constant for site 1 are faster than that for site
2. Similar to the response kinetics, for a xed temperature T, site 1
yields faster recovery than site 2. At lower temperatures, probably
the recovery trends for these two sites are reversed. Based on the
above ndings, nally it is argued that macro-porous regions of the
sensing elements are responsible to yield faster response as well as
recovery kinetics as compared to regions with meso-porous struc-
tures. The results are also indicative to the fact that the natures of
the chemi-absorbed oxygen species are also different in these two
different adsorption sites.
Acknowledgments
The above research work is partially supported by the research
grant from Department of Information Technology vide grant No.
20(7)2006-NANO. One of the authors (Mr. Kalisadhan Mukhejee)
also wishes to acknowledge the partial nancial support through
a JRF fellowship from the Council of Scientic and Industrial
Research. We would like to thank Mr. Rajasekhar for the magnetic
measurements of the samples.
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