Ecotoxicology and Environmental Safety ()

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Ecotoxicology and Environmental Safety

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

Fabrication of zirconia composite membrane by in-situ hydrothermal

technique and its application in separation of methyl orange
R. Vinoth Kumar, Aloke Kumar Ghoshal, G. Pugazhenthi n
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India

art ic l e i nf o

a b s t r a c t

Article history:
Received 2 December 2014
Received in revised form
4 May 2015
Accepted 6 May 2015

The main objective of the work was preparation of zirconia membrane on a low cost ceramic support
through an in-situ hydrothermal crystallization technique for the separation of methyl orange dye. To
formulate the zirconia lm on the ceramic support, hydrothermal reaction mixture was prepared using
zirconium oxychloride as a zirconia source and ammonia as a precursor. The synthesized zirconia powder
was characterized by X-ray diffractometer (XRD), N2 adsorption/desorption isotherms, Thermogravimetric analysis (TGA), Fourier transform infrared analysis (FTIR), Energy-dispersive X-ray (EDX) analysis
and particle size distribution (PSD) to identify the phases and crystallinity, specic surface area, pore
volume and pore size distribution, thermal behavior, chemical composition and size of the particles. The
porosity, morphological structure and pure water permeability of the prepared zirconia membrane, as
well as ceramic support were investigated using the Archimedes method, Field emission scanning
electron microscopy (FESEM) and permeability. The specic surface area, pore volume, pore size distribution of the zirconia powder was found to be 126.58 m2/g, 3.54 nm and 0.310 mm, respectively. The
porosity, average pore size and pure water permeability of the zirconia membrane was estimated to be
42%, 0.66 mm and 1.44
10  6 m3/m2 s kPa, respectively. Lastly, the potential of the membrane was investigated with separation of methyl orange by means of ux and rejection as a function of operating
pressure and feed concentration. The rejection was found to decrease with increasing the operating
pressure and increases with increasing feed concentrations. Moreover, it showed a high ability to reject
methyl orange from aqueous solution with a rejection of 61% and a high permeation ux of
2.28
10  5 m3/m2 s at operating pressure of 68 kPa.
& 2015 Elsevier Inc. All rights reserved.

Keywords:
Zirconia membrane
Methyl orange
Hydrothermal treatment
Dye removal

1. Introduction
The annual global productions of dyes are calculated to be more
than ten thousand tons. In that, around 15% quantity is lost during
the industrial processes, such as dyeing, textiles printing and dye
manufacturing (Forgacs et al., 2004). These industrial processes
utilize several synthetic chemical dyes for a variety of purposes.
Textile dyeing is among the most environmentally unfriendly industrial processes owing to the large quantities of water demanded and the strongly colored wastewater produced, polluted
with dyes and other chemical auxiliaries. The highly colored efuents dye streams could pose serious detrimental effects to the
environment and thus to human health (Zaghbani et al., 2007;
Jana et al., 2010). Specically, Azo dyes can be toxic upon degradation and this class of dye is widely used in many industries
by virtue of present unique properties and technical
n

characteristics. Among several varieties of dyes, methyl orange

(MO) is considered as a model compound for ordinary water soluble azo dyes, which is extensively utilized in chemical, textile
and paper industries. Furthermore it is dangerous to the environment (Shiue et al., 2012). The majority of the azo dyes and
their breakdown products are toxic and carcinogenic to animals
and humans (Weisburger, 2002). Hence, this efuent is necessary
to be treated before discharging from the industries. The conventional methods employed for separation of dyes from colored
wastewater are occulation/coagulation (Zahrim and Hilal, 2013),
adsorption (Qiao et al., 2009), chemical oxidation (Turgay et al.,
2011) and photocatalytic processes (Velusamy et al., 2014), reaction with ozone (Sharma et al., 2013) and biological treatment
(Nilesh and Chaudhari, 2006). In occulation, coagulation and
adsorption treatment methods, efuents are converted from the
liquid state to a solid state and this way creates secondary

Corresponding author. Fax: 91 361 2582291.

E-mail address: pugal@iitg.ernet.in (G. Pugazhenthi).

http://dx.doi.org/10.1016/j.ecoenv.2015.05.006
0147-6513/& 2015 Elsevier Inc. All rights reserved.

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i

R.V. Kumar et al. / Ecotoxicology and Environmental Safety ()

pollution. Chemical techniques such as photocatalytic and reaction

with ozone method need bulk quantity of costly chemicals as well
as generating huge amount of waste slurry. The by-products from
chemical degradation are also colored and even toxic. Furthermore, biological degradation is inexpensive technique, harmless to
the environment and also not generates massive quantities of
sludge; however it is selective and time taking. Hence it is unsuitable for many dyes (Tan et al., 2006).
Membrane separation process could be ecofriendly and an
auspicious alternative for the separation of dyes. The pressuredriven membrane processes, especially reverse osmosis, nanoltration, ultraltration and microltration are being increasingly
utilized in the removal of dyes (Al-Bastaki, 2004; Kim et al., 2005;
Al-Aseeri et al., 2007; Mo et al., 2008). Within these techniques,
ceramic membranes are better than polymeric membranes due to
excellent thermal, chemical and mechanical properties (Jedidi
et al., 2009). However, nanoltration and reverse osmosis techniques are described by higher energy utilization. Therefore lower
pressure membrane techniques such as microltration and ultraltration could be inexpensively more favorable for dye separation. Besides, ceramic membranes are made up of a composite
formation with an active top layer, which typically decide its separation characteristics. Mostly the active top layers are made by
inorganic oxides fabricated via the solgel method, dip-coating,
hydrothermal crystallization with a controlled particle size. Initially, the research on inorganic membranes was focused to the
fabrication of alumina membranes, which is of higher cost and
used most widely (Yang et al., 1998). Nevertheless, in recent times,
various other porous membrane materials, such as zirconia, titania
and silica were used. Amongst these, zirconia is especially attractive material for making the ceramic membranes. The excellent
characteristics of zirconia membrane are elevated chemical stability and cleaning actions can be done in the range of 014 pH,
superior permeability and higher ux in separation owing to its
specic surface characteristics, and excellent thermal resistance
(Bhave, 1991).
In order to improve the ux of the membrane, the hydrophilic
adaptation in microltration is an excellent choice, which provides
an enhanced hydrophilic character to the membrane surface (Kocherginsky et al., 2003). Nano-scale ZrO2, TiO2/Al2O3, Al2O3 and
SiO2 have been used to enhance the hydrophilic character and it
creates the charge on the surface of the membrane (Chang et al.,
2014). Several investigations on zirconia membrane have indicated
its superior performance in the separation due to its special surface character (Zhou et al., 2010). These hydrophilic and charged
membranes facilitate to attain a higher ux with good separation
efciency even though utilizing a realistically larger range of pore
size membranes. However, the difculty of modication of ceramic
membranes leads in the way of adding nano-particles uniformly
into the porous ceramic membrane without blocking the membrane pores. Several preparation methods have been developed,
such as in situ hydrothermal synthesis, vapor phase transport
method, secondary growth method for the deposition of nanomaterials on the ceramic matrix (Xu et al., 2004). Amongst these,
hydrothermal technique has become basic route for the modication of membrane surface by the deposition of nanomaterial
(Kalantari et al., 2015).
In this present study, an inexpensive zirconia composite
membrane on a porous ceramic support has been synthesized. The
top layer of zirconia is prepared through in-situ hydrothermal
crystallization technique by controlling growth of zirconia particle
on the porous ceramic support. The separation potential of the
membrane is investigated with separation of methyl orange various operating pressure and feed concentration.

2. Materials and methods

2.1. Chemicals
Clays (ball clay, feldspar, kaolin, pyrophyllite and quartz) used
for synthesis of ceramic support were of mineral grade and obtained in the vicinity (Kanpur, India). Zirconium Oxychloride
(ZrOCl2  H2O), Calcium Carbonate and Polyvinyl Alcohol (PVA)
were supplied by Loba Chemie (Mumbai). Ammonium hydroxide
solution (NH4OH, 25 wt%) and methyl orange (C14H14N3NaO3S)
were procured form from Merck (I) Ltd. (Mumbai).
2.2. Preparation of zirconiaceramic composite membrane
The procedure followed for the preparation of ceramic support
and its composition were explained in our earlier publication
(Monash and Pugazhenthi, 2011a). The zirconiaceramic composite membrane was prepared through in-situ hydrothermal
synthesis by controlling growth of zirconia particle on the porous
ceramic support. The reaction mixture for hydrothermal reaction
was prepared by dissolving 5 g of zirconium oxychloride in 100 mL
of water. Then the pH was adjusted to 10.0 with addition of aqueous ammonia (25%) under stirring condition at room temperature. After that the reaction mixture was stirred vigorously for
5 min, and then transferred to Teon coated stainless steel autoclave reactor (capacity 200 mL) for in-situ hydrothermal crystallization and a prepared porous ceramic support having 43 mm
diameter and 4.5 mm thickness was placed inside the reactor. The
reaction mixture was subjected to hydrothermal crystallization at
90 C for 60 h. After that, the membrane was recovered and washed several times with Millipore water and dried at 90 C for 24 h
followed by calcined at 400 C for 6 h in air atmosphere.
2.3. Methods for characterization
2.3.1. Characterization of zirconia powder
As-synthesized zirconia powder was collected from the bottom
of the autoclave reactor. Then, the zirconia powder was washed,
dried and calcined at the same condition adopted for the composite membrane. Precise powder diffraction data of zirconia was
measured on a machine (Bruker AXS D8 advanced) with Cu K
( 1.5406 ) radiation. The patterns were obtained in the 2
range of 575 with a scan speed of 0.05 s  1. N2 adsorption/
desorption isotherm was computed at  196 C in a surface area
analyzer (make: Beckman-Coulter; model: SA 3100). Thermogravimetric (TGA) analysis of the zirconia powder (before calcination) was carried out in a instrument of Mettler Toledo with
model No.TGA/SDTA 851s in owing nitrogen atmosphere at a
heating rate of 10 C min  1 from 25 to 900 C. FTIR spectra were
recorded using a Shimadzu IRAfnity-1 model Spectrometer in the
wavenumber range of 4000500 cm  1. The particle size distribution (PSD) of the zirconia powder was measured using a
machine Malvern Mastersizer 2000 (APA 5005s model, hydro
MU) in wet dispersion mode.
2.3.2. Characterization of zirconia ceramic composite membrane
The morphology of the prepared ceramic support and zirconia
composite membrane was investigated with an instrument FESEM
(JEOL JSM-5600LV). Energy-dispersive X-ray (EDX) was carried out
using SEM (LEO 1430 VPs Oberkochen, Germany). In order to
determine the porosity, the membrane was dried at 120 C for 3 h
and measured the dry weight of the membrane (MD). Then the
membrane was placed in Millipore water for 24 h. After which, the
wet weight (MW) of the membrane was determined after removing all visible water from the surface of the membrane with tissue
paper. Then the membrane was immersed in water, the pore lled

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i

R.V. Kumar et al. / Ecotoxicology and Environmental Safety ()

MWMD
=
MWMA

(1)

2.3.3. Pure water permeability and microltration of methyl orange

(MO)
The in-house made dead-end ltration setup with capacity of
250 ml was used to determine the water ux and pure water
permeability presented as supplementary data (see Fig. S1). It
consists of two parts, a cylindrical top part and a base plate with a
provision to keep a membrane. The membrane was placed on a
perforated casing and then kept in the bottom compartment. The
upper compartment of the batch cell was pressurized using nitrogen gas by setting a desired pressure through regulator attached with the nitrogen cylinder. The water ux was calculated at
various applied pressures. At every applied pressure, the collection
of rst 50 mL of permeate was disposed and time taken for collection of following 50 mL of permeate was noted for the determination of ux. The following relations were used to calculate
the water ux and pure water permeability.

JW =

Q
= L p P
A T

(2)

where, JW is the water ux (ms  1), Q is the volume of water

permeated (m3), A is the effective membrane area (m2), T is the
sampling time (s). LP is water permeability (ms  1 kPa  1) and P is
applied pressure (kPa).
The average pore size was determined using Hagen Poiseuille
expression assuming that pores are cylindrical in shape (Almandoz
et al., 2004; Bowen et al., 1997; Kumar et al., 2015).

JW =

r 2P
= L p P
8l

(3)

where, is the porosity of the membrane, r is the pore radius of

the membrane, l is the pore length, is the tortuosity factor and
is the viscosity of water.
The separation potential of the membrane was evaluated by
undertaking the separation tests of methyl orange using the same
setup lled with 100 mL of the feed solution. In order to determine
the permeate ux at xed operating pressure, initial 10 mL of the
collected permeate was disposed and the time needed to collect
subsequent 10 mL of permeate was calculated. The observed rejection was evaluated by the following expression.

R=

Cf CP
100
Cf

(4)

where, R is the observed rejection (%), Cf is the concentration of

the feed solution and Cp is the concentration of the permeate solution. After carrying out a preliminary calibration procedure, the
precise concentration of dye was determined by measuring the
absorbance of the dye at a wavelength of 472 nm using a UVvis
spectrophotometer (Spectrascan, UV 2300) (Monash and Pugazhenthi, 2014). After every experimental run, the membrane was
thoroughly washed with Millipore water, followed by ushing
with Millipore water at higher pressure to regain the original pure
water ux.

3. Results and discussion

3.1. Characterization of zirconia powder
X-ray diffraction analysis of fumed zirconia powder shows the
tetragonal phase along with some small peaks of the monoclinic
phase (Fig. 1). The patterns with a wide base line illustrate the
presence of amorphous zirconia. As a whole, zirconia powder is
packed with both amorphous and nano-crystals. Crystallite size of
the zirconia powder is calculated by DebyeScherrer formula
(D K/ cos ), in which K ( 0.90) stands for shape factor,
(0.15406 nm) represents the wave length of X-rays, is the full
width of diffraction peak at half-maximum intensity in radians,
and is the Bragg angle. The crystallite size of the zirconia is found
to be in the range of 5.5414.31 nm. The bigger crystal size is due
to the thermally activated crystal growth. This result is in accordance with previous results published in the literature (Wu and
Cheng, 2000; Etienne et al., 1994; Gestel et al., 2006). N2 adsorptiondesorption isotherm is depicted in Fig. 2(a). It clearly represents type IV adsorption isotherm with H-2 hysteresis loop
according to IUPAC classication and associated with capillary
condensation in the mesopores (Sangwichien et al., 2002). The
pore size distribution of the zirconia is calculated from desorption
branch of isotherm by BJH model. In Fig. 2(b), the distribution
curve indicates that the most of the pores are present with a size
smaller than 10 nm and the sample possesses a relatively narrow
size distribution. BET surface area and pore diameter are estimated
to be 126.58 m2/g, and 3.54 nm, respectively.
Thermogravimetric analysis is carried out for the as-synthesized zirconia powder (gure not shown). The total weight loss is
estimated to be approximately 21%. In general, the weight loss at
temperature below 150 C is owing to elimination of weekly adhered water molecule that was absorbed by the sample. The
weight loss at higher temperature is attributed to removal of
structural hydroxyl groups. Moreover, the weight loss of the particle after 450 C is found to be insignicant. This justies the
selection of calcination temperature for the synthesis membrane.
Fig. 3 demonstrates the FTIR spectra of zirconia (both before and
after calcination). Before calcination, OH stretching and bending
band appear at around 3400 and 1600 cm  1, respectively. These
bands are related to adsorbed water, and illustrate the [ZrO(OH)2]n

H2O polymer structure. A sharp band at 1000 cm  1 describes Zr O
group stretching vibration, indicating that Zr O bond is not
50

40
tetragonal- ZrO2

30
Intensity

with water saturated weight of the membrane (MA) was measured

(A refers to Archimedes). The porosity of the membrane was estimated according to the below expression (Monash and Pugazhenthi, 2011b).

tetragonal- ZrO2

20

monoclinic- ZrO2

10

0
10

20

30

40
50
2 (Degrees)

60

70

Fig. 1. XRD pattern of zirconia powder.

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i

R.V. Kumar et al. / Ecotoxicology and Environmental Safety ()

9
Before calcination

60

40

20
Adsorption Isotherm
Desorption Isotherm

Transmittance (a.u.)

80

-1

Volume adsorbed [cc g (STP) ]

100

7
16
After calcination

14
12

0
0.0

0.2

0.4
0.6
0.8
Relative pressure P/Po

1.0

8
4000 3500 3000 2500 2000 1500 1000
Wavenumbers (cm-1)

0.035
0.030
d(V P )/d(D P ) (ml/g.nm)

10

500

Fig. 3. FTIR analysis of zirconia powder.

0.025
0.020
0.015
0.010
0.005
0.000
10

100
Pore diameter (nm)

Fig. 2. (a) N2 adsorptiondesorption isotherms and (b) BJH pore size distribution of
zirconia.

converted into ZrO bond. The calcined zirconia shows absorption

peak around at 800 cm  1, which is typically monoclinic zirconia. Zr
O bonds exhibit bands at 450520 cm  1 whereas a broad infrared
band at 520 cm  1 exhibits tetragonal ZrO2 phase (Chandra et al.,
2010; Wong et al., 2002). The particle size distribution analysis was
measured for the synthesized zirconia powder. It is found that the
size of the particles is in the ranges of 0.310 mm as shown in supplementary data (see Fig. S2). Moreover, the volume median diameter (d0.5) is calculated to be 2.237 mm.
3.2. Characterization of ceramic support and zirconia composite
membrane
The porosity of the prepared ceramic support and zirconia
composite membrane is measured to be 44%, and 42%, respectively. The average pore size is estimated to be 0.969 mm and
0.66 mm for support and composite membrane, respectively. It is
inferred from these values that, the porosity and pore radius of the
zirconia membrane are reduced after hydrothermal treatment
owing to the deposition of zirconia particles on the surface of the
support. Fig. 4(a), illustrates the FESEM image of fabricated support and it is apparent that the uniform surface is highly porous

and crack free. Fig. 4(b) shows the deposition of fumed zirconia on
to the surface of the membrane. It indicates that the lm of zirconia is deposited on the pore of ceramic support. Hence it can be
concluded that the ziconia is formed on the surface of the membrane support with smooth consistent surface. In addition, the
pore density of the membrane is estimated from SEM micrographs
using Image J software. In order to minimize errors of image
analysis, three SEM micrographs are analyzed for each sample. The
pore density of the ceramic support and zirconia membrane is
found to be 2.34
106 and 3.80
105 pore/mm2, respectively. The
decreased pore density for the zirconia membrane is due to the
blockage of pores by the formation of zirconia particles on the
surface of ceramic support.
Fig. 4(b) (inside) depicts an EDX spectrum, which quantitatively
detects the constituent elements. The spectrum shows Zr peaks
signifying the existence of zirconia on the composite membrane.
Other peaks detected in the EDX spectrum include oxygen, which
also derived from the deposition of ziconia. Fig. 5 depicts the pure
water ux of ceramic support along with zirconia membrane. As
expected water ux increases linearly with an increase of applied
pressure and follows Darcy's law. It is observed that the water ux
is lower than that of ceramic support, which is accredited by reduction in pore radius on hydrothermal treatment. As a result, the
pure water permeability of zirconia membrane reduces resulting
in lower ux. The pure water permeability (Lp) for support and
zirconia membrane is found to be 3.63
10  6 and
1.44
10  6 m3/m2 s kPa, respectively.
Table S1 (presented as supplementary data) summarizes the
overall properties of the fabricated ceramic support and zirconia
membrane. As stated above, the porosity, water permeability,
mean pore size and pore density of the zirconia membrane is
decreased (see Table S1), which is obviously due to the incorporation of the zeolite particles on the ceramic support by
hydrothermal treatment.
3.3. Microltration of methyl orange
3.3.1. Effect of operating pressure
The ux and rejection trend of MO solution with different operating pressures (69207 kPa) at a xed concentration

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i

R.V. Kumar et al. / Ecotoxicology and Environmental Safety ()

Fig. 4. (a) FESEM image of ceramic support and (b) zirconiaceramic composite membrane with EDX.

0.0010

Zirconia-ceramic membrane
Ceramic support

Water flux (m3/m2s)

0.0008

0.0006

0.0004

0.0002

0.0000
0

50

100

150

200

250

300

350

Applied pressure (kPa)

Fig. 5. Variation of water ux with applied pressure for support and zirconia
membrane.

(1000 ppm) is shown in Fig. 6(a). The permeate ux increases with

increasing operating pressure, due to the increase of driving force
across the membrane. However, the permeate ux is lesser than
that of pure water ux. This may be due to various aspects such as
adsorption of dye particles on the surface of membrane and pores,
and concentration polarization. The dye particles are settled on the
membrane surface or into the pores, which raise membrane
fouling and resulting in reduction in permeate ux (Benitez et al.,
2009). The observed rejection slightly decreases with an increase
of applied pressure. It means that the membrane properties have
little effect on the dye removal with operating pressure. The removal of MO dye is perhaps due to the surface charge of zirconia
membrane. The isoelectric point (IEP) of zirconia is reported to be
4 (Seshadri et al., 1998; Tsuru et al., 1998). It signies that the
zirconia membrane is positively charged at pHo 4 and negatively
charged at pH 44. Therefore the prepared composite membrane is
negatively charged as the natural pH of dye solution used in this
work is 5.7. It can be claried that the repulsion between membrane surface and the anionic dye molecule in the aqueous solution causes the removal of MO in the permeate.
3.3.2. Effect of feed concentration
The effect of feed concentrations (10003000 ppm) of MO on

Fig. 6. (a) Effect of operating pressure and (b) feed concentration on methyl orange
separation.

the permeate ux and rejection was investigated at a constant

pressure of 69 kPa and the obtained results are depicted in Fig. 6
(b). As anticipated, the ux decline is high at higher concentration
as the feed concentration raises the membrane fouling severely.

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i

R.V. Kumar et al. / Ecotoxicology and Environmental Safety ()

An increase in dye adsorption on the membrane surface and

concentration polarization might be the responsible factors for this
observation (Cassano et al., 2008). The obtained rejection data at
these concentrations demonstrate that the rejection slightly increases with increasing the feed concentration. At higher concentration, the transportation of MO through the membrane is
reduced due to the retention of MO in the deposit on the membrane surface. MO agglomerates more rapidly when the concentration of MO in the feed solution is high (Monash et al., 2010);
as a result, concentration of MO in the permeate declines.

4. Conclusions
The zirconiaceramic composite membrane has been successfully prepared by in-situ hydrothermal crystallization with controlled growth of zirconia particle on the porous ceramic support.
XRD analysis of zirconia powder calcined at 450 C reveals the
presence of tetragonal phase along with some small peaks of the
monoclinic phase of zirconia. EDX spectrum demonstrates the
presence of the zirconia in the membrane FESEM image veries
that the zirconia particles adhere on the surface of the membrane.
Moreover, porosity, average pore size and pure water permeability
of the zirconia membrane is estimated to be 42%, 0.66 mm and
1.44
10  6 m3/m2 s kPa, respectively. Separation potential of the
prepared membrane is investigated on the effect of parameters
such as operating pressure and feed concentration and its inuences on both permeate ux and MO removal is discussed.
Moreover, the highest separation (61%) is obtained with the
permeate ux of 2.28
10  5 m3/m2 s at 68 kPa for the feed concentration of 3000 ppm.

Acknowledgment
We would like to thank the Central Instrument Facility, IIT
Guwahati for helping us to perform FESEM analysis. This work was
nancially supported by a research grant under the Fast Track
Scheme (SR/FTP/ETA-44/2010) from Department of Science and
Technology (DST), Government of India.

Appendix A. Supplementary information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.ecoenv.2015.05.
006.

References
Al-Aseeri, M., Bu-Ali, Q., Haji, S., Al-Basataki, N., 2007. Removal of acid red and
sodium chloride from aqueous solutions using nanoltration. Desalination 206,
407413.
Al-Bastaki, N., 2004. Removal of methyl orange dye and Na2SO4 salt from synthetic
waste water using reverse osmosis. Chem. Eng. Process. 43, 15611567.
Almandoz, M.C., Marchese, J., Pradanos, P., Palacio, L., Hernandez, A., 2004. Preparation and characterization of non-supported microltration membranes
from aluminosilicates. J. Membr. Sci. 241, 95103.
Benitez, F.J., Acero, J.L., Real, F.J., Garcia, C., 2009. Removal of phenyl-urea herbicides
in ultrapure water by ultraltration and nanoltration processes. Water Res. 43,
267276.
Bhave, R.R., 1991. Inorganic Membranes Synthesis, Characteristics and Applications.
Van Nostrand Reinhold, New York.
Bowen, W.R., Mohammad, A.W., Hilal, N., 1997. Characterisation of nanoltrtation
membranes for predictive purposes-use of salts uncharged solutes and atomic
force microscopy. J. Membr. Sci. 126, 91105.
Cassano, A., Mecchia, A., Drioli, E., 2008. Analyses of hydrodynamic resistances and
operating parameters in the ultraltration of grape must. J. Food Eng. 89,
171177.

Chandra, N., Singh, D.K., Sharma, M., Upadhyay, R.K., Amriphale, S.S., Sanghi, S.K.,
2010. Synthesis and characterization of nano-sized zirconia powder synthesized by single emulsion-assisted direct precipitation. J. Colloid Interface Sci.
342, 327332.
Chang, Q., Zhou, J., Wang, Y., Liang, J., Zhang, X., Cerneaux, S., Wang, X., Zhu, Z.,
Dong, Y., 2014. Application of ceramic microltration membrane modied by
nano-TiO2 coating in separation of a stable oil-in-water emulsion. J. Membr. Sci.
456, 128133.
Etienne, J., Larbot, A., Julbe, A., Guizard, C., Cot, L., 1994. A microporous zirconia
membrane prepared by the solgel process from zirconyl oxalate. J. Membr. Sci.
86, 95102.
Forgacs, E., Cserhati, T., Oros, G., 2004. Removal of synthetic dyes from wastewaters:
a review. Environ. Int. 30, 953971.
Gestel, T.V., Kruidhof, H., Blank, D.H.A., Bouwmeester, H.J.M., 2006. ZrO2 and TiO2
membranes for nanoltration and pervaporation Part 1. Preparation and
characterization of a corrosion-resistant ZrO2 nanoltration membrane with a
MWCOo300. J. Membr. Sci. 284, 128136..
Jana, S., Purkait, M.K., Mohanty, K., 2010. Removal of crystal violet by advanced
oxidation and microltration. Appl. Clay Sci. 50, 337341.
Jedidi, I., Saidi, S., Khemakhem, S., Larbot, A., Elloumi-Ammar, N., Fourati, A., Char,
A., Salah, A.B., Amar, R.B., 2009. Elaboration of new ceramic microltration
membranes from mineral coal y ash applied to waste water treatment. J.
Hazard. Mater. 172, 152158.
Kalantari, N., Vaezi, M.J., Yadollahi, M., Babaluo, A.A., Bayati, B., Kazemzadeh, A.,
2015. Synthesis of nanostructure hydroxy sodalite composite membranes via
hydrothermal method: support surface modication and synthesis method
effects. AsiaPac. J. Chem. Eng. 10, 4555.
Kim, T.H., Park, C., Kim, S., 2005. Water recycling from desalination and purication
process of reactive dye manufacturing industry by combined membrane ltration. J. Clean. Prod. 13, 779786.
Kocherginsky, N.M., Tan, C.L., Lu, W.F., 2003. Demulsication of water-in-oil
emulsion via ltration through a hydrophilic polymer membrane. J. Membr. Sci.
220, 117128.
Kumar, R.V., Basumatary, A.K., Ghoshal, A.K., Pugazhenthi, G., 2015. Performance
assessment of an analcimeC zeoliteceramic composite membrane by removal
of Cr(VI) from aqueous solution. RSC Adv. 5, 62466254.
Mo, J.H., Lee, Y.H., Kim, J., Jeong, J.Y., Jegal, J., 2008. Treatment of dye aqueous solutions using nanoltration polyamide composite membranes for the dye
wastewater reuse. J. Dyes Pigm. 76, 429434.
Monash, P., Majhi, A., Pugazhenthi, G., 2010. Separation of bovine serum albumin
(BSA) using -Al2O3clay composite ultraltration membrane. J. Chem. Technol.
Biotechnol. 85, 545554.
Monash, P., Pugazhenthi, G., 2011. Development of ceramic supports derived from
low-cost raw materials for membrane applications and its optimization based
on sintering temperature. Int. J. Appl. Ceram. Technol. 8, 227238.
Monash, P., Pugazhenthi, G., 2011. Effect of TiO2 addition on the fabrication of
ceramic membrane supports: a study on the separation of oil droplets and
bovine serum albumin (BSA) from its solution. Desalination 279, 104114.
Monash, P., Pugazhenthi, G., 2014. Utilization of calcined Ni-Al layered double hydroxide (LDH) as an adsorbent for removal of methyl orange dye from aqueous
solution. Environ. Prog. Sustain. Energy 33, 153159.
Nilesh, P.T., Chaudhari, S., 2006. Degradation of azo dyes by sequential Fentons
oxidation and aerobic biological treatment. J. Hazard. Mater. B 136, 698705.
Qiao, S., Hu, Q., Haghseresht, F., Hu, X., Lu, G.Q., 2009. An investigation on the adsorption of acid dyes on bentonite based composite adsorbent. Sep. Purif.
Technol. 67, 218225.
Sangwichien, C., Aranovich, G.L., Donohue, M.D., 2002. Density functional theory
predictions of adsorption isotherms with hysteresis loops. Colloids Surf. A 206,
313320.
Seshadri, K.S., Ahamed, J., Kesavamoorthy, R., Srinivasan, M.P., Krishnasamy, V.,
1998. Estimation of pore charge on zirconia membrane prepared by solgel
route using zeta potential measurement. J. Mater. Sci. Technol. 14, 425428.
Sharma, S., Buddhdev, J., Patel., M., Ruparelia, J.P., 2013. Studies on degradation of
reactive red 135 dye in wastewater using ozone. Procedia Eng. 51, 451455.
Shiue, A., Ma, C., Ruan., R., Chang, C., 2012. Adsorption kinetics and isotherms for
the removal methyl orange from wastewaters using copper oxide catalyst
prepared by the waste printed circuit boards. Sustain. Environ. Res. 22,
209215.
Tan, X., Kyaw, N.N., Teob, W.K., Li, K., 2006. Decolorization of dye-containing aqueous solutions by the polyelectrolyte-enhanced ultraltration (PEUF) process
using a hollow ber membrane module. Sep. Purif. Technol. 52, 110116.
Tsuru, T., Takezoe, H., Asaeda, M., 1998. Ion separation by porous silicazirconia
nanoltration membranes. AIChE J. 44, 765768.
Turgay, O., Ersoz, G., Atalay, S., Forss., J., Welander., U., 2011. The treatment of azo
dyes found in textile industry wastewater by anaerobic biological method and
chemical oxidation. Sep. Purif. Technol. 79, 2633.
Velusamy, P., Pitchaimuthu, S., Rajalakshmi, S., Kannan, N., 2014. Modication of the
photocatalytic activity of TiO2 by b-cyclodextrin in decoloration of ethyl violet
dye. J. Adv. Res. 5, 1925.
Weisburger, J.H., 2002. Comments on the history and importance of aromatic and
heterocyclic amines in public health. Mutat. Res. Fundam. Mol. Mech. Mutagen.
506507, 920.
Wong, M.S., Huang, H.C., Ying, J.Y., 2002. Supramolecular-templated synthesis of
nanoporous zirconiasilica catalysts. Chem. Mater. 14, 19611973.
Wu, J.C., Cheng, L., 2000. An improved synthesis of ultraltration zirconia membranes via the solgel route using alkoxide precursor. J. Membr. Sci. 167,

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i

R.V. Kumar et al. / Ecotoxicology and Environmental Safety ()

253261.
Xu, X., Bao, Y., Song, C., Yang, W., Liu, J., Lin, L., 2004. Microwave-assisted hydrothermal synthesis of hydroxy-sodalite zeolite membrane. Microporous Mesoporous Mater. 75, 173181.
Yang, C., Zhang, G., Xu, N., Shi, J., 1998. Preparation and application in oilwater
separation of ZrO2/-Al2O3 MF membrane. J. Membr. Sci. 142, 235243.
Zaghbani, N., Haane, A., Dhahbi, M., 2007. Separation of methylene blue from
aqueous solution by micellar enhanced ultraltration. Sep. Purif. Technol. 55,
117124.

Zahrim, A.Y., Hilal, N., 2013. Treatment of highly concentrated dye solution by
coagulation/occulationsandltration and nanoltration. Water Resour. Ind. 3,
2334.
Zhou, J., Chang, Q., Wang, Y., Wang, J., Meng, G., 2010. Separation of stable oilwater
emulsion by the hydrophilic nano-sized ZrO2 modied Al2O3 microltration
membrane. Sep. Purif. Technol. 75, 243248.

Please cite this article as: Kumar, R.V., et al., Fabrication of zirconia composite membrane by in-situ hydrothermal technique and its
application in separation of methyl orange. Ecotoxicol. Environ. Saf. (2015), http://dx.doi.org/10.1016/j.ecoenv.2015.05.006i