Synthesis and characterization of ZrO2 nanoparticles by an arc discharge method in water

Article abstract of DOI:10.1080/15533174.2011.568423

ZrO₂ nanoparticles were produced by high current electrical arc discharge of zirconium electrodes in deionized (DI) water. A mixture of nanocrystalline ZrO₂ monoclinic and tetragonal phase form based on X-ray diffraction (XRD) analysis. Dynamic light scattering (DLS) result indicates that the size of the particles increases by increasing the arc current. Absorption spectroscopy of the samples shows a red shift on absorption edge by increasing the arc current. Band gap of the produced ZrO₂ nanoparticles at 10 A arc current corresponds to 5.4 eV, which decreases to 5 eV by increasing the arc current up to 20 A. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.568423

This article was downloaded by: [University of Chicago Library]
On: 06 October 2014, At: 08:48
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer
House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
Synthesis and Characterization of ZrO2 Nanoparticles
by an Arc Discharge Method in Water
Ali Akbar Ashkarran a , Seyed Mahyad Aghigh a , Seyedeh Arezoo Ahmadi Afshar a , Mona
Kavianipour a & Mahmoud Ghoranneviss a
a Plasma Physics Research Center, Science and Research Branch, Islamic Azad
University , Tehran, Iran
Published online: 25 May 2011.
To cite this article: Ali Akbar Ashkarran , Seyed Mahyad Aghigh , Seyedeh Arezoo Ahmadi Afshar , Mona Kavianipour &
Mahmoud Ghoranneviss (2011) Synthesis and Characterization of ZrO2 Nanoparticles by an Arc Discharge Method in Water,
Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:5, 425-428
To link to this article: http://dx.doi.org/10.1080/15533174.2011.568423
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall
not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other
liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:425–428, 2011
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.568423
Synthesis and Characterization of ZrO2 Nanoparticles by an
Arc Discharge Method in Water
Ali Akbar Ashkarran, Seyed Mahyad Aghigh, Seyedeh Arezoo Ahmadi Afshar,
Mona Kavianipour, and Mahmoud Ghoranneviss
Plasma Physics Research Center, Science and Research Branch, Islamic Azad University,
Tehran, Iran
simplicity of this method also allows scaling up for mass
production.
The early works by arc discharge method in liquids
ZrO2 nanoparticles were produced by high current electrical
arc discharge of zirconium electrodes in deionized (DI) water. A
mixture of nanocrystalline ZrO2 monoclinic and tetragonal phase
form based on X-ray diffraction (XRD) analysis. Dynamic light
scattering (DLS) result indicates that the size of the particles in-
creases by increasing the arc current. Absorption spectroscopy of
the samples shows a red shift on absorption edge by increasing the
arc current. Band gap of the produced ZrO2 nanoparticles at 10
A arc current corresponds to 5.4 eV, which decreases to 5 eV by
increasing the arc current up to 20 A.
were based on production of MWCNTs,[8–11] SWCNTs and
SW-CNHs,[9] and nano-onions.[11] In recent years, few articles
have been published regarding synthesis of nanoparticles such
as MoS2,[12] CuO and Cu2O,[13] Ag,[14,15] Au,[16] WO3,[17] and
ZnO[18] by arc discharge in liquids.
In this work, we have prepared ZrO2 nanoparticles by arc
discharge method in DI water for the first time and studied the
effect of arc current on size distribution and optical properties
of the produced particles. To the authors’ knowledge, to date no
published scientific work has been reported regarding synthesis
of ZrO2 nanoparticles by high current arc discharge in water.
In fact, the most important advantage of this method is direct
formation of zirconium dioxide nanoparticles from zirconium
metal in DI water, which is necessary for some applications in
liquid medium.
Keywords arc discharge, DI water, photocatalytic activity, ZrO2
nanoparticles
INTRODUCTION
ZrO2 is a wide band-gap (5.0–5.5 eV) transition metal oxide
with excellent mechanical, thermal, optical, and electrical
characteristics.[1] It can be widely used in the fabrication of
structural ceramic devices, gas sensors, catalysts, and optoelec-
tronic devices.[2–4] So the preparation and properties of ZrO2
have been extensively and intensively studied. By far, a variety
of physical and chemical techniques including hydrothermal,[5]
sol-gel,[6] chemical vapor deposition (CVD),[7] and sputtering[3]
have been developed to synthesize ZrO2 nanoparticles. Among
physical and chemical methods, electrical arc discharge in
liquid is an attractive method because of simplicity of apparatus
building, no need for complicated vacuum equipments, low
impurity introduction, high-throughput, and cost-effective
procedure to generate a high yield of nanoparticles. The
EXPERIMENTAL
The preparation system consists of two main parts as we have
reported in our previous works.[15,17] A high current DC power
supply and a reactor including anode, cathode, and a micrometer
that moves the anode towards the cathode. In this work, 10 to
20 A current was applied between two zirconium electrodes.
The voltage was dropped to about 2 to 3.5 V during the arc
while the current was fixed to desired amount. Both anode and
cathode were wire shaped 1 mm in diameter and 99.2% purity
(from Goodfellow). Initially, the two electrodes were brought
into touch leading to a small contact cross section and thus to
a high current density. Then we separate them from each other,
and as a result, zirconium is ablated from the anode and then
condensed in water.
The crystalline structure was characterized by a XRD diffrac-
tometer (X’pert Philips) with wavelength of Cu Kα radiation be-
ing 1.5406 Å in 2ꢀ range from 10◦ to 80◦ by 0.04◦ sec-1 steps.
UV-Vis spectroscopy of the samples was taken by a Lambda 950
spectrophotometer (Perkin Elmer). Size distribution of nanopar-
ticles was determined by a Zetasizer Nano ZS from Malvern
Received 27 November 2009; accepted 4 February 2011.
This work was supported by Plasma Physics Research Center, Sci-
ence and Research Branch, Islamic Azad University and the authors
would like to thank the Research Council of Islamic Azad University
for financial support.
Address correspondence to Ali Akbar Ashkarran, Plasma Physics
Research Center, Science and Research Branch, Islamic Azad Uni-
versity, P.O. Box 14665-678, Tehran, Iran. E-mail: ashkarran@srbiau.
ac.ir
425

426
A. A. ASHKARRAN ET AL.
FIG. 1. XRD pattern of ZrO2 nanoparticles was made at 10 A arc current.
(Figure is provided in color online.)
FIG. 2. DLS results for as prepared nanoparticles at 10, 15, and 20 A electrical
arc current. (Figure is provided in color online.)
company. SEM analysis was done by a Philips XL30 instru-
ment at 20 kV accelerating voltage by deposition of ZrO2
nanoparticles onto the Si (100) substrate at room temperature.
DI water was supplied from a Millipore water purification
system (Direct-Q-3) with 18.2 Mꢁ-cm (0.055 µs) resis-
tance.
metry of size distribution diagrams in DLS analysis illustrates
uniformity of the formed nanoparticles. The data clearly reveals
broadening of size distribution and increase of average parti-
cles size distribution by increasing the arc current. The reason
for this behavior has been discussed in detail in our previous
work.[17]
SEM Analysis
RESULTS AND DISCUSSION
Microscopic structure of the samples was found by SEM
analysis. Figure 3 illustrates ZrO2 SEM image at 10 A cur-
rent. Although size measurement is slightly difficult from the
image due to agglomeration of particles but we can conclude
the particles distributed uniformly and size of the particles is
in agreement with DLS result for the 10 A sample. The size
XRD Analysis
Crystalline phase and structure of the produced nanoparticles
were found by XRD analysis. The result for sample prepared
at 10 A arc current shows formation of crystalline ZrO2 with a
mixture of monoclinic and tetragonal phase, which is depicted
in Figure 1. The obtained spectrum has the ZrO2 monoclinic
phase peaks at 2ꢀ = 24.5, 28.2, 31.5, 35.3, 50.2, 50.7, 60.1,
62.8, 72.9, 73.5, and 74.6 degrees and tetragonal phase peaks at
2ꢀ = 30.2, 34.6, and 59.3 degrees, which is in agreement with
the 37–1484 and 42–1164 standard card from the JCPDS. The
single crystalline size determined by Debye-Scherrer formula
was 26.5 nm. This result corresponds to other works such as
Zhang et al.[19] and Liang et al.[20]
DLS Analysis
DLS analysis was taken out to find the size of the pro-
duced nanoparticles. Figure 2. demonstrates DLS results of
ZrO2 nanoparticles obtained at three different arc currents. Size
distribution of the particles formed at 10 A arc current shows
formation of nanoparticles with average size of 32 nm and dis-
tribution about 12 nm. By increasing the arc current to 15 and
20 A, the size distribution is broadened and the average size
is increased to 50 and 78 nm, respectively. Rather good sym-
FIG. 3. SEM image of as prepared ZrO2 nanoparticles at 10 A arc current.

SYNTHESIS AND CHARACTERIZATION OF ZrO2 NANOPARTICLES
427
FIG. 4. (a) Optical absorption of as prepared ZrO2 nanoparticles and red shift on absorption edge (the inset diagram), and (b) (αhυ)1/2 versus the hυ diagram for
ZrO2 nanoparticles at 10, 15, and 20 A arc currents. (Figure is provided in color online.)
obtained by DLS and SEM analysis is bigger than the size ob- duce ZrO2 nanoparticles, especially for applications that need
tained from XRD. In fact, the particle size in XRD analysis a liquid medium. Further investigations on ZrO2 nanoparticles,
represents the average size of crystallites and not that of the such as their photocatalytic activity and other physiochemi-
produced particles. This shows that the produced particles are cal properties, are undergoing and will be reported in the near
polycrystalline in nature.
future.
CONCLUSION
Optical Properties Studies
In summary, we have prepared ZrO2 nanoparticles in one step
by the high current electrical arc discharge method in DI water
for the first time. XRD analysis illustrates formation of a mix-
ture of nanocrystalline ZrO2 monoclinic and tetragonal phase
and 26.5 nm single crystalline domain size. DLS measurements
show formation of nanoparticles with average size of 32 nm for
10 A arc current which grow to 50 and 78 nm by increasing
the arc current to 15 and 20 A, respectively. SEM images of
as prepared sample at 10 A arc current demonstrate rather fine
and uniform particles in nanometer range. Optical absorption
of ZrO2 nanoparticles at 10 A arc current shows an absorption
edge about 300 nm that has a red shift by increasing the arc
current. The calculated band gap for the samples prepared at 10
A arc current was 5.4 eV, which decreased to 5 eV by increasing
the arc current to 20 A.
Optical properties of ZrO2 nanoparticles were measured by
UV-Vis spectroscopy. Figure 4a demonstrates absorption spectra
of as prepared nanoparticles in DI water. It shows an absorp-
tion edge about 300 nm, which shifts to higher wavelengths by
increasing the arc current (the inset diagram). In the high ab-
sorption region, absorption coefficient (α), is related to incident
photons by the relation αhυ = A(hυ-Eg)η,[17] where A is a con-
stant and η is an index that characterizes the optical absorption
process and is theoretically equal to 1/2, 2, 3/2, and 3 for direct
allowed, indirect allowed, direct forbidden, and indirect forbid-
den transitions, respectively. Since ZrO2 is an indirect band gap
semiconductor, the (αhυ)1/2 versus the hυ diagram is depicted
in Figure 4b. The tangent line on the curve shows the energy
band gap of the nanoparticles and is corresponding to 5.4 eV at
10 A arc current. By increasing the arc current to 15 and 20 A,
the band gap decreases to 5.15 and 5 eV, respectively. In fact,
by increasing the arc current, the size of the nanoparticles in-
creases and band gap decreases. These values are in agreement
with other works obtained by different methods such as sol-gel
and chemical,[6,21]
REFERENCES
1. Grover, V.; Shukla, R.; Tyagi, A.K. Facile synthesis of ZrO2 powders:
Control of morphology. Scr. Mater. 2007, 57, 699–702.
2. Tahir, M.N.; Gorgishvili, L.; Li, J.; Gorelik, T.; Kolb, U.; Nasdala, L.;
Tremel, W. Facile synthesis and characterization of monocrystalline cubic
ZrO2 nanoparticles. Solid State Sci. 2007, 9, 1105–1109.
3. Rozoa, C.; Jaque, D.; Fonseca, L.F.; Garcia Sole, J. Luminescence of rare
earth-doped Si–ZrO2 co-sputtered films. J. Lumin. 2008, 128, 1197–1204.
Results showed that electrical arc discharge in water is a
promising method for fabrication of ZrO2 nanoparticles in one
step from zirconium electrodes. This will enable us to easily pro-

428
A. A. ASHKARRAN ET AL.
4. Liang, L.; Xu, Y.; Wu, D.; Sun, Y.A simple sol–gel route to ZrO2 films
with high optical performances. Mater. Chem. Phys. 2009, 114, 252–
Liquid phase arc discharge process. J. Phys. Chem. B 2005, 109, 14011–
14016.
256.
14. Loa, C.H.; Tsung, T.T.; Lin, H.M. Preparation of silver nanofluid by the
submerged arc nanoparticle synthesis system (SANSS). J. Alloys Compd
2007, 434–435, 659–662.
15. Ashkarran, A.A.; Iraji zad, A.; Ahadian, M.M.; Hormozi Nezhadi, M.R.
Stability, size and optical properties of colloidal silver nanoparticles pre-
pared by electrical arc discharge in water. Eur. Phys. J. Appl. Phys., 2009,
48, 10601–10607
5. Seok Lee, W.; Woog Kim, S.; Heon Koo, B.; Sik Bae, D. Synthesis and
microstructure of Y2O3-doped ZrO2–CeO2 composite nanoparticles by
hydrothermal process. Colloids Surf., A. 2008, 313–314, 100–104.
6. Ehrhart, G.; Capoen, B.; Robbe, O.; Boy, P.; Turrell, S.; Bouazaoui, M.
Structural and optical properties of n-propoxide sol–gel derived ZrO2 thin
films. Thin Solid Films 2006, 496, 227–233.
7. Torres-Huerta, A.M.; Dominguez-Crespo, M.A.; Ramirez-Meneses, E.;
Vargas-Garcia, J.R. MOCVD of zirconium oxide thin films: Synthesis and
characterization. Appl. Surf. Sci. 2009, 255, 4792–4795.
16. Lung, J.K.; Huang, J.C.; Tien, D.C.; Liao, C.Y.; Tseng, K.H.; Tsung, T.T.;
Kao, W.S.; Tsai, T.H.; Jwo, C.S.; Lin, H.M.;l Stobinski, L. Preparation
of gold nanoparticles by arc discharge in water. J. Alloys Compd 2007,
434–435, 655–658.
8. Lange, H.; Sioda, M.; Huczko, A.; Zhub, Y.Q.; Krotob, H.W.; Walton,
D.R.M. Nanocarbon production by arc discharge in water. Carbon 2003, 17. Ashkarran, A.A.; Iraji zad, A.; Ahadian, M.M.; Mahdavi Ardakani, S.A.
41, 1617–1623.
Synthesis and photocatalytic activity of WO3 nanoparticles prepared by
the arc discharge method in deionized water. Nanotechnology 2008, 19,
195709–195715.
9. Sano, N.; Nakano, J.; Kanki, T. Synthesis of single-walled carbon nanotubes
with nanohorns by arc in liquid nitrogen. Carbon 2004, 42, 667–691.
10. Sano, N.; Wang, H.; Alexandrou, I.; Chhowalla, M.; Teo, K.B.K.; Ama-
ratunga, G.A.J. Properties of nanocarbon particles produced by an arc dis-
charge in water. J. Appl. Phys 2002, 92, 2783–2788.
11. Sano, N.; Wang, H.; Chhowalla, M.; Alexandrou, I.; Amaratunga, G.A.J.
Synthesis of carbon onions in water. Nature 2001, 414, 506–507.
12. Alexandrou, I.; Sano, N.; Burrows, A.; Meyer, R.R.; Wang, H.; Kirkland, A.;
Kiely, C.J.; Amaratunga, G.A.J. Structural investigation of MoS2 core–shell
18. Ashkarran, A.A.; Iraji zad, A., Mahdavi, S.M.; Ahadian, M.M. ZnO
nanoparticles prepared by electrical arc discharge method in water. Mater.
Chem. Phys. 2009, 118, 6–8.
19. Zhang, Y.W.; Sun, X.; Xu, G.; Yan, C.H. Doping effects of Yb3+ on the
crystal structures, nanoparticle properties and electrical behaviors of ZrO2
derived from a facile urea-based hydrothermal route. Solid State Sci. 2004,
6, 523–531.
nanoparticles formed by an arc discharge in water. Nanotechnology 2003, 20. Liang, J.; Jiang, X.; Liu, G.; Deng, Z.; Zhuang, J.; Li, F.; Li, Y. Character-
14, 913–917.
ization and synthesis of pure ZrO2 nanopowders via sonchemical method.
Mater. Res. Bull. 2003, 38, 161–168.
21. Liang, L.; Xu, Y.; Wu, D.; Sun, Y. A simple sol–gel route to ZrO2 films
with high optical performances. Mater. Chem. Phys. 2009, 114, 252–256.
13. Yao, W.T.; Yu, S.H.; Zhou, Y.; Jiang, J.; Wu, Q.S.; Zhang, L.; Jiang,
J. Formation of uniform CuO nanorods by spontaneous aggregation:
selective synthesis of CuO, Cu2O, and Cu nanoparticles by a solid-