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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 10457–10463
www.elsevier.com/locate/ceramint

Hollow mesoporous zirconia nanocontainers for storing and controlled

releasing of corrosion inhibitors
Arunchandran Chenan, S. Ramya, R.P. George, U. Kamachi Mudalin
Corrosion Science and Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, India
Received 8 February 2014; accepted 4 March 2014
Available online 17 March 2014

Abstract

Release of inhibitor molecules on demand from nanocontainers dispersed in a passive barrier coatings offer great promise for active corrosion
protection coatings of metals and alloys with self healing ability. In the present study, hollow mesoporous zirconia nanospheres (hm-ZrO2) with
a hollow core/porous shell structure are proposed as effective containers for corrosion inhibitor loading and releasing. Hollow mesoporous
zirconia nanocontainers were synthesized using solid silica nanoparticles as templates. The morphology and phase of zirconia nanocontainers
were studied using high resolution transmission electron microscopy and laser Raman spectroscopy. 2-Mercaptobenzothiazole was selected as
the model corrosion inhibitor for the encapsulation. The storage and release properties of hm-ZrO2 were investigated using UV–visible
spectroscopy. The encapsulation efficiency of hm-ZrO2 was 63% and we observed a faster and higher release of 2-MBT from hm-ZrO2 when the
pH was shifted
from neutral value.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Calcination; C. Corrosion; C. Diffusion; D. ZrO2

1. Introduction nCorresponding author. Tel.: þ91 44 2748 0121; fax: þ91 44 2748 0301.
E-mail addresses: [email protected],
Corrosion of metals and alloys is a global problem resulting
[email protected] (U. Kamachi Mudali).
in huge economic loses and causing environmental concerns.
Application of coatings on metals and alloys are one of the http://dx.doi.org/10.1016/j.ceramint.2014.03.016
most effective methods employed to prevent corrosion [1]. 0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
The main attribute of anticorrosion coatings is to avoid the undesired leaching of inhibitors and inhibitor deactivation [2–7].
contact of metals from its environment and they function But this disadvantage can be smartly overcome by the
either passively or actively. In passive corrosion protection, encapsulation of corrosion inhibitor in nanocontainers and
coatings act as an impermeable physical barrier to the uniformly dispersing them in the coating. These nanocontainers
corrosive environment. However, these class of coatings work dispersed in the coating can release inhibitor on demand during
only when the coatings remain intact. Any damage in the corrosion process and protect the underlying metal. Many
coatings will lead to corrosion. On the contrary, in active encapsulation techniques have been reported so far for effective
corrosion protection corrosion inhibitors are incorporated in storage and on demand release of corrosion inhibitors. Emulsion
the barrier coatings and corrosion inhibition would be initiated polymerization encapsulation, layer by layer assembly of
when the barrier coating is damaged [2]. The corrosion oppositely charged polyelectrolyte and inhibitor layers on the
inhibitors cannot be added directly into the barrier coatings, as surface of nanoparticles and adsorption of inhibitor molecules on
it can disrupt coating integrity due to the porous metal oxides are some of the encapsulation
techniques reported [4–7]. This smart strategy helps in storing
10458 A. Chenan et al. / Ceramics International 40 (2014) 10457–10463

the inhibitor and thereby avoiding any unfavorable interaction of corrosion inhibitor, acetone was used for inhibitor loading
inhibitor with the coating. Nanocontainers are used to load high experiments and sodium chloride (NaCl) was used for releasing
amount of inhibitor, avoid detrimental leaching of inhibitor and experiments. All the chemicals used were of reagent grade and
ensure sustained and intelligent release of inhibitor on demand. the water used in the study was purified in a three stage Millipore
The release of inhibitor is induced by changes in the local Milli-Q plus 185 purification system, which had a resistivity
environment in the damaged area of the coating, such as changes higher than 18 MΏ. cm.
in local pH, ionic strength, or presence of aggressive ions [8].
Heterocyclic organic compounds consisting of oxygen, nitrogen, 2.2. Preparation of SiO2 template particles
sulfur, and phosphorus are generally used as corrosion inhibitors.
2-mercaptobenzothiazole, a thiazole derivative, was chosen as The stober method was used to synthesize monodispersed
model inhibitor molecule for encapsulation in this study. silica nanoparticles [20]. 75 mL of ethanol, 10 mL of water and
Zheludkevich et al. employed silica nanoparticles covered 3.15 mL of concentrated ammonia solution were mixed and
layer-by-layer with polyelectrolyte and layers of inhibitor as stirred. After 30 minutes of stirring, 6 mL of TEOS was added
nanocontainer for active corrosion protection [2]. Even though a dropwise and the reaction mixture was stirred for 8 h. The
layer-by-layer assembled shell could ensure sustained release of resultant white silica powders were collected by centrifugation
inhibitor molecules for active corrosion protection, their and washed several times with water and ethanol. Then the solid
complexities limit the scaling up and industrial application. silica powders were again dispersed in water and dried at room
These difficulties can be overcome by using hollow and porous temperature.
nanomaterials with high pore volume and large surface area to
load corrosion inhibitors. Porous metal oxides have been
successfully employed as nanocontainers to encapsulate 2.3. Preparation of hm-ZrO2
corrosion inhibitors. Recently, inorganic porous materials have
been widely investigated as reservoirs for loading corrosion 2 g of SiO2 template particles were dispersed in 200 mL
inhibitors [9–16]. Compared to porous metal oxides and of ethanol and 1 mL Brij 30 and 1 mL water was added into
inorganic porous materials, hollow mesoporous nanomaterials it. After 30 min of stirring of the reaction mixture, 6 mL of Zr
can function as a better container for encapsulation. The hollow (BuO)4 was added and the mixture was further stirred for 8 h.
inner cavity of these porous nanomaterials can effectively store The white colored powder was collected after centrifugation
the inhibitor molecules and release in a controlled way through and redispersed in water. These particles were aged in water
its mesopore channels. for 3 days at 298 K and this aging step has a very important
This work describes a new contribution to the design of role on the structure of the shell. After aging, the removal of
nanocontainer for the encapsulation of corrosion inhibitor. the organic material and the crystallization of the amorphous
Hollow mesoporous zirconia nanocapsules with a hollow core / zirconium oxide layer were carried out by calcination. The
porous shell structure were synthesized through a hard template white powder was calcined at 850 1C for 2 h. Finally, the silica
method [17–19]. In this method, the size and the size distribution templates were removed by a treatment with NaOH (5 M) for
of the hollow spheres are controlled by the size of the template. 48 h. The powders were kept in NaOH solution with stirring
The template is then removed through the pores of the final and after 24 h NaOH solution was exchanged with fresh
spheres obtained. Monodispersed solid silica nanoparticles were alkaline solution and the stirring continued for another 24 h.
used as template for the synthesis of hm-ZrO2. The silica After removing the silica template, the core-shell zirconia
nanoparticles were coated with zirconium oxide layer and later spheres were washed five times with water and dried at 100
these silica templates were removed using sodium hydroxide. 1C for further use.
The present study reports the synthesis, characterization and
inhibitor storage and release properties of hollow mesoporous
zirconia spheres. 2.4. Characterization of hm-ZrO2

2. Experimental section The high resolution images of silica template and hm-ZrO2
were taken using a JEOL JEM 2100 (Japan) electron
2.1. Materials microscope operated at 200 kV. The powder samples were
dispersed in ethyl alcohol under ultrasonication and few drops
All chemicals were used as received without further
of the dispersed samples were placed on the sample holder and
purification. Zirconium butoxide solution (80 wt. % in 1-
analyzed without further treatment. The phase analysis of the
butanol), tetraethoxysilane (TEOS), ethanol, concentrated hm-ZrO2 was carried out using laser Raman spectroscopy
ammonia solution (25% NH3 in water), sodium hydroxide (Lab RAM HR 800, HORIBA JOBIN YVON Raman
(NaOH), and Brij 30 were used to synthesize hollow mesoporous spectrometer equipped with 1800 grooves/mm holographic
zirconia spheres. 2-mercaptobenzothiazole (MBT) was used as grating). The sample was placed under Olympus BXFM-ILHS
 A. Chenan et al. / Ceramics International 40 (2014) 10457–10463 10459

microscope mounted at the entrance of the Raman in the preparation of hollow mesoporous zirconia are
spectrograph. Arþ laser of 488 nm was used as excitation described below.
source and the power of the laser at the sample was 8.6 mW.
The Raman spectra wereo recorded using a super cooled ( 110 1. Monodispersed silica template nanoparticles were
1C) 1024 256 pixels charge coupled detector (CCD) in static synthesized using the well known stober method.
mode over the range of 80–1000 cm1 with 10 s exposure time 2. The prepared monodispersed silica nanoparticles were
and 10 CCD accumulations. Nitrogen adsorption/desorption thencoated with amorphous layer of zirconium hydroxide
isotherms were recorded at 77 K on a Sorptomatic 1990 during the hydrolysis of zirconium butoxide in the presence
(Thermo Quest, CE Instruments, Italy).The specific surface of Brij 30.
area was calculated by Brunauer–Emmett–Teller (BET) 3. The silica core with the zirconia shell containing Brij 30 was
aged in water for 3 days at room temperature.
method [21]. The HMS sample was first degassed for 24 h at
4. Later the silica core with zirconia shell was calcined at850 1C
150 1C in vacuum. The average pore size and pore size
to remove the organics and to achieve the crystallization of
distributions were obtained from the desorption branch using
the shell.
Barrett–Joyner–Halenda (BJH) method [22].
5. Finally, the template, silica core was removed using NaOH(5
2.5. Loading and releasing of 2-MBT
M) treatment for 48 h. The silica particles were leached out
through the pores present in the zirconia shell. The removal
50 mg of hm-ZrO2 was mixed with 3 mL of 1 mg mL1 MBT
of solid silica core particles resulted in the formation of
solution. The mixture was then sonicated for 30 m and stirred
hollow mesoporous zirconia nanocontainers.
further for 24 h in a glass vial. After 24 h of stirring of the
mixture, the nanocontainers loaded with inhibitor molecules
were taken out by centrifugation and cleaned with water. The
MBT loaded hm-ZrO2 was obtained by drying at room Fig. 1 depicts the HRTEM images of silica template particles
temperature. The filtrate was extracted from the vial and used having average diameter of 375 nm. Fig. 2 presents the HRTEM
for UV-visible spectroscopy studies to confirm the images of hollow mesoporous zirconia obtained after the
encapsulation of MBT. UV–visible spectroscopy (UV-2450, removal of silica templates. As presented in the HRTEM images,
SHIMADZU make, Japan) was used for UV–vis analysis. the average thickness of zirconia layer was 30 nm. The perfectly
25 mg of MBT loaded hm-ZrO2 was dispersed in 150 mL of shaped spherical morphology of the zirconia nanocontainer was
releasing medium (0.05 M NaCl) at different pH values of 3, maintained after calcination and the removal of silica template
7 and 10 at room temperature and the solution was stirred at a with NaOH treatment (Fig. 2). The porous structure of the shell
rate of 500 rpm using a magnetic stirrer. 1 mL of the solution helped the NaOH solution to access the core of the nanocontainer
was pipetted out at given time intervals for UV-visible and dissolve the silica. The removal of silica particle from the
analysis. After the measurement, the solution was poured back interior confirmed that the zirconia nanocontainer had a porous
immediately to the solution. structure. As shown in the HRETM image (Fig. (2d)) the
hollowness was the most important structural feature of the as
prepared zirconia nanospheres. Both the porous structure and
3. Results and discussion hollowness are very essential for high loading capacity of the
inhibitor molecules. During encapsulation, the pores on the shell
3.1. Synthesis and characterization of hm-Zirconia spheres facilitate the diffusion of the inhibitor molecules and the empty
space inside the zirconia sphere facilitates the storage of
Hollow mesoporous zirconia nanocontainers with
inhibitor molecules. Moreover, the porous structure of the shell
approximate size of 400 nm were synthesized using a modified makes ease on demand release of the inhibitor molecules.
method published elsewhere [17–19]. The five steps involved The phase of the as prepared hollow mesoporous zirconia was
investigated using laser Raman spectroscopy. Fig. 3 shows
10460 A. Chenan et al. / Ceramics International 40 (2014) 10457–10463

Fig. 1. HRTEM images of solid silica nanoparticles at different magnifications.

Fig. 2. HRTEM images of hollow mesoporous zirconia nanocontainers at different magnifications.

 A. Chenan et al. / Ceramics International 40 (2014) 10457–10463
10461

Fig. 3. Raman spectra of as prepared hollow mesoporous zirconia. g1. The high surface area, mesopore distributions and hollow
structure of the nanocontainer are very important for inhibitor
the Raman spectrum of hollow mesoporous zirconia. As loading and controlled inhibitor release properties.
revealed by Fig. 3, the characteristic phonon modes of tetragonal
phase of zirconia were observed in the Raman spectra. Five 3.2. Inhibitor loading and releasing properties of hm-ZrO2
Raman active modes of tetragonal phase were observed. The nanocontainers
bands at 149 cm1, 274 cm1, and 463 cm1 are assigned to the Eg
mode of vibration of tetragonal phase [23]. The bands at 318 cm1 2-Mercaptobenzothiazole was successfully loaded into
and 648 cm1 were of hmZrO2 nanocontainers by mixing hm-ZrO2 nanocontainers
B1g mode. with 2-MBT solution in acetone and followed by stirring for
The mesoporosity of the sample was confirmed by N2 24 h. Fig. 5 presents the UV–vis spectra of MBT solution
adsorption-desorption isotherm analysis presented in Fig. 4. before and after the interactions with hm-ZrO2
nanocontainers. λmax for

2-mercaptobenzothiazole is at 325 nm. The UV–visible spectra

Fig. 4. N2 adsorption-desorption isotherms of hm-ZrO2 and pore size (Fig. 5) showed that, the absorption maxima for 2-MBT was
distribution (inset). decreased after the interaction of MBT molecules with hm-ZrO2
nanocontainers. Moreover, there were no new absorption bands
The hollow zirconia particles showed a sorption isotherm of and the position of the peaks was not changed. This decrease in
type IV with a hysteresis loop characteristic for materials with the absorption intensity of MBT after the interaction with hm-
mesoporous structure. The hysteresis loop was due to the ZrO2 nanocontainers confirmed the decrease of the MBT
capillary condensation in mesopore structures. The type IV concentration in the solution as well as the successful loading of
adsorption isotherm is a characteristic feature of mesoporous the MBT molecules in the pores and interiors of hm-ZrO2
materials. The specific surface area of hollow zirconia nanocontainers. The loading of the organic inhibitor molecules
products was obtained using the BET method and it was found in inorganic nanocontainers are made possible through weak non
to be 145.97 m2 g1. Barrett–Joyner–Halenda (BJH) analyses covalent interactions such as physical adsorption, electrostatic
revealed that the hollow zirconia products exhibited pore size interaction, hydrogen bonding and π–π stacking [19]. The
centered at 3.9 nm and cumulative pore volume of 0.0993 cm3 loading efficiency was calculated as follows:
Fig. 5. UV–visible spectra of MBT before and after interaction with hm-ZrO2.
 10462 A. Chenan et al. / Ceramics International 40 (2014) 10457–10463

Loading efficiency ð%Þ

¼ðTotal amount of MBTFree MBT in solution= Total

amount of MBTÞ 100

The loading efficiency of MBT in the HMS nanocontainer

was found to be 63%.
The release behavior of 2-MBT loaded hm-ZrO2 was
investigated by UV–visible analysis of NaCl (0.05 M)
suspensions of 2-MBT loaded hm-ZrO2 at different pH values.
The absorption intensity at ca. 325 nm was measured at given
time interval for 28 h and the results are shown in Fig. 6.
Fig. 6 shows the release of MBT and the increase of
concentration of MBT with time and attained equilibrium after
5 h. When the releasing medium had infiltrated into the pores
and channels of hm-ZrO2 nanocontainers, the inhibitor
molecules (2-MBT) gets dissolved in the medium and released
by diffusion through the pores along the aqueous pathways.

Fig. 6. UV–vis spectra at different times of the 0.05 M NaCl media in which 2-MBT was released from 2-MBT loaded hm-ZrO2 nanocontainers (a) at pH 3, (b) at
pH 7, (c) at pH 10 and (d) corresponding pH-dependent releasing behavior of 2-MBT from hm-ZrO2-MBT system.

The releasing of MBT from hm-ZrO2 followed similar release explained by the variation of solubility of MBT and the
kinetics at different pH values. A faster release was observed differences in the surface charge of both MBT and zirconia
under alkaline and acidic conditions compared to neutral particles with pH. The solubility of 2-MBT is low in neutral pH,
condition. The release of MBT was leveled off and reached but relatively higher in alkaline and acidic conditions [24]. Both
equilibrium in 4 h at pH 10. the zirconia particles and the inhibitor molecules have the same
It was observed that higher amount of 2-MBT was released surface charge when the pH values vary from neutral pH values.
from the hm-ZrO2 at pH 3 and 10 compared to pH 7. The amount Under acidic pH conditions zirconia particles have positive
of MBT released after 28 h under acidic and alkaline conditions surface charge whereas; at alkaline pH zirconia particles acquire
were 0.66 mg mL1 and 0.53 mg mL1 respectively, while in negative surface charge [25]. At acidic pH, MBT could be
neutral conditions it was 0.45 mg mL1 only. The difference in the protonated due to the presence of a lone pair of electrons on the
release rate and quantity of MBT released from hm-ZrO2 can be N atom and carries a positive charge [26,27]. Thus under acidic
 A. Chenan et al. / Ceramics International 40 (2014) 10457–10463 10463

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