Ionics DOI 10.

1007/s11581-011-0646-z

ORIGINAL PAPER

Synthesis, micro-structural, and electrical analysis on lanthanum fluoride

D. Arun Kumar & S. Selvasekarapandian & H. Nithya & M. Hema

Received: 13 September 2011 / Accepted: 9 November 2011 # Springer-Verlag 2011

Abstract Lanthanum fluoride nanorod and nanoparticles have been synthesized by a simple method with and without sonication, respectively. Thermogravimetric/differential thermal analysis confirms the sample formation at low temperature for the sonication-assisted sample than the directly prepared sample. The structure of the prepared lanthanum fluoride nanorods and nanoparticles has been analyzed by X-ray diffraction studies and the microstructural properties have been studied using transmission electron microscopy. The transmission electron microscopic image reveals a capsule-like shape for the sample prepared under sonication. Ion conduction and conductivity analysis of the prepared nanorods and nanoparticles has been studied using AC impedance spectroscopy, and the ionic conductivity was found to increase by an order for the sample prepared with sonication. Keywords Anionic conductors . Ionic conductivities . Sensors . XRD . AC . Conductivities
D. A. Kumar : S. Selvasekarapandian Department of Physics, Bharathiar University, Coimbatore 641 046, India D. A. Kumar : H. Nithya DRDO-BU Center for Life Sciences, Bharathiar University, Coimbatore 641 046, India S. Selvasekarapandian (*) Kalasalingam University, Krishnankoil, Srivilliputhur 626 190 Tamil Nadu, India e-mail: sekarapandian@yahoo.com M. Hema Kamaraj College of Engineering, Virudhunagar, Tamil Nadu, India

Introduction Nowadays, due to the increase in pollution of the environment, new materials are to be explored to study and monitor the environment surrounding us. Solid electrolyte sensors are good electrolytes and offer excellent potential for use in electrochemical sensors [1]. Rare earth ionic conductors are widely used as sensors in applications such as critical care, medicine, emissions monitoring, etc. Among them, rare earth fluorides exhibit high ionic conductivity at ambient temperature than other rare earth materials. Lanthanum fluoride exhibits high ionic conductivity at ambient temperatures among other rare earth fluorides [2, 3]. Lanthanum fluoridebased chemical sensors have been applied for sensing fluoride, oxygen, and carbon monoxide because of its high chemical stability and high ionic conductivity [47]. Wu and Heitjans et al. have reported that the ionic conductivity increases by an order when the particle size is in the nanoscale when compared with the single crystal [8, 9]. Recently, LaF3 thin films with particle size ranging from 50 to 90 nm were prepared by vacuum evaporation and LaF3 powders with particle size ranging from 100 to 200 nm had been synthesized by microwave heating method, microemulsion method, and hydrothermal method, and the results indicated that LaF3 nanoparticles could increase its ionic conductivity [1013]. Sonochemical technique is an easier method to prepare nanoparticles by reduction of metallic ions, which is remarkably activated by the ultrasonic irradiation-induced cavitations. Ultrasonic-assisted process has been proven to be a useful technique in the synthesis of novel materials. Cerium fluoride nanostructures have been prepared by ultrasonically assisted route by Yang Liu et al. [14]. To our knowledge, there are no reports for the preparation of lanthanum fluoride under ultrasonication. The chemical

Ionics

effects of ultrasound arise from acoustic cavitation involving the formation, growth, and collapse of bubbles in liquid [15], which generates localized hot spots having a temperature of roughly 5,000 K, pressure of about 20 Mpa, and very high cooling rates of about 107 Ks1 [16]. In the present work, nanocrystalline lanthanum fluoride has been synthesized by a simple method of direct precipitation [17] from aqueous solution with and without sonication. Since the effect of sonication on the ionic conductivity of nanoparticles has not been reported elsewhere, an attempt has been made to study the effect of sonication on ionic conductivity of the prepared lanthanum fluoride nanoparticles for their potential application in sensors.

Experimental method Lanthanum nitrate (La (NO3)36H2O) and ammonium fluoride (NH4F) were purchased from Merck and HiMedia, respectively, and used without further purification. Lanthanum fluoride nanoparticles were prepared by adding 0.3 mol/L lanthanum nitrate dissolved in nanopore water to 1 mol/L ammonium fluoride dissolved in nanopore water. The lanthanum fluoride nanoparticles are formed instantly while adding the fluoride solution to the nitrate solution. The possible reaction is given below: LaNO3 3 3NH4 F ! LaF3 3NH4 NO3 1

300 C for 24 h and without sonication was calcined at 350 C for 24 h. The sample prepared under sonication was labeled as LFA and the sample prepared without sonication was labeled as LF. The resultant powder was then pressed into pellets of 1 cm in diameter and thickness of 1 mm using a hydraulic press for electrical measurements. Thermogravimetric/differential thermal analysis (TG/DTA) has been carried out using Perkin Elmer STA 6000 to confirm the formation temperature of the sample. The X-ray diffraction analysis of the calcined lanthanum fluoride nanoparticles has been done using a PANalytical Xpert Pro with CuK1 radiation as the source material. Transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM) and selected area electron diffraction (SAED) measurements for the as-prepared and annealed samples have been carried out using TECHNAI G20-stwin (200 kV) with a point resolution of 1.44 and line resolution of 2.32 . AC impedance spectroscopic analyses were performed using a computer-controlled HIOKI 3532 LCZ meter within the frequency range 42 Hz to 4 MHz at different temperatures and using stainless steel as the blocking electrodes.

Results and discussion TG/DTA analysis Figure 1 shows the TG/DTA traces of the as-prepared LaF3 precursors prepared with and without sonication. From the traces, a slight endothermic peak at around 100200 C accompanied with a small weight loss in the TG curve is ascribed to the removal of water from the precursor and the broad endothermic peak at around 230 and 290 C accompanied with a drastic weight loss in the TG curve of the precursors LFA and LF can be ascribed to the removal of nitrate present in the precursor. The TG curve confirms the formation temperature of the sample to be at 230 and 290 C for the samples prepared with sonication and without sonication, respectively. The sample prepared under sonication forms at low temperature and this may be attributed to the energy acquired by the sample during sonication. It is well known from the literature that an ultrasonic pulse generates hot bubbles that create hot spots during the collapse of hot bubbles [15]. These hot spots when interacting with the sample generate high temperature, which plays a vital role in the formation of the nanoparticles at low temperatures. From the TG results, the samples prepared with and without sonication were calcined at 300 and 350 C, respectively. Structural analysis The X-ray diffractogram of the prepared lanthanum fluoride nanoparticles is shown in Fig. 2. The XRD pattern shows a

The experiment was extended to study the effect of sonication. In the typical sonication process, the two solutions were made to dissolve with the beaker kept in a sonication bath. The frequency of the sonicator is 40 kHz and the power is 120 W. The actual power delivered for the reaction system was calculated by thermal method. For this purpose, the aforesaid sonochemical reaction was repeated without any control on temperature. The rate of change of temperature (dT/dt) was monitored every 1 h. The power at every time instance was calculated by the following relationship: Power delivered dT =dt V Cp 2

where V refers to the volume of the reaction mixture (100 ml) and Cp refers to the specific heat capacity of water. Such calculations resulted in the power of 1.5 to 0.5 W from 0 s up to 60 min, respectively. At 60 min, the reaction temperature became constant at around 45 C. So, the average power delivered to the system could be considered as slightly less than 1 W. The nanoparticles thus obtained without sonication and with sonication were washed with double-distilled water several times and dried under vacuum for 2 h. The nanoparticles prepared under sonication were calcined at

Ionics Fig. 1 TG/DTA of LaF3 prepared a with sonication (LFA) and b without sonication (LF)

a
50

b
LFA
100 95

300

LF

100 90

DTA V Endo Up

40

DTA V Endo Up

90

Weight %

85 30 80 75 20 70 65 10 100 200 300

o

70 100 60 50 40 100 200 300

o

60

Temperature C

Temperature C

sharp, well-defined, and high intensity peak for the samples prepared with and without sonication. All the peaks match with JCPDS card no. 320483 and with the earlier results reported [17, 18]. Along with the peaks observed for the samples prepared without sonication, well-resolved peaks at 2 values 24.34 (002), 40.46 (211), 49.73 (004), 57.26 (222), 73.84 (224), 74.59 (412), and 78.08 (006) are observed. This may be due to the increase in the crystalline nature of the samples due to the effect of sonication. The lattice parameters calculated from the XRD spectra were a= 7.18 , b=7.18 , and c=7.34 for the sample prepared with sonication and a=7.17 , b=7.17 , and c=7.35 for the samples prepared without sonication. The system is found to be in primitive hexagonal structure. The average
Fig. 2 XRD pattern of sample prepared (a) with sonication, (b) without sonication, and (c) standard LaF3 (JCPDS 320483)
3000

particle size has been calculated using the Scherrer formula given by [19]: D 0:94l b2q cos q 3

where l 2 wavelength of the X-ray source full width at half-maxima diffraction angle

The average particle size calculated using the Scherrer formula is found to be 17 and 19 nm for the sample prepared with (LFA) and without sonication (LF).

(111)

(a)
(300) (113) (220)

LFA

2000
(002) (110)

(221)

(112)

(114) (222)

(223)

1000

(304) (410) (411)

(224) (412)

(211)

0 250

Intensity

200 150
(110)

(111)

(300) (113)

(b) LF
(302) (221) (223) (304) (115) (411)

100 50 0 100 80 60 40 20 0 10 20

(112)

(c)

JCPDS 320483

30

40

50

60

70

degree

(006)

80

Weight %

200

80

Ionics

Nanostructural analysis (TEM and HRTEM) The morphology and the nanostructure of the prepared lanthanum fluoride nanoparticles have been studied using transmission electron microscopic analysis. Figure 3a, b shows the TEM images of the as-prepared samples obtained by sonication and without sonication. Figure 3c, d shows the HRTEM images of the samples prepared with and without sonication. From the TEM images, the sample prepared with sonication shows nanorod-like structures, which is due to the influence of sonication, and the TEM images of the sample prepared without sonication shows no specific morphology. The
Fig. 3 TEM images of the asprepared samples a with sonication and b without sonication. HRTEM images of the asprepared samples c with sonication and d without sonication. SAED pattern of the as-prepared samples e with sonication and f without sonication

average particle size is calculated to be 19 and 38 nm for the sample prepared with and without sonication, respectively. The aspect ratio of the as-prepared nanorods was found to be 2.67 (sample prepared with sonication). From the HRTEM images, the lattice spacing d has been calculated and found to be 3.08 and 3.012 for the sample prepared with and without sonication, respectively, which matches with the (111) plane of lanthanum fluoride in the hexagonal structure. Figure 3e, f shows the SAED pattern for the sample prepared with and without sonication, respectively. The SAED pattern confirms the polycrystalline nature of the prepared samples. The d spacing values have been calculated and the results

(a) LFA

(b) LF

(c)

(d)

(e)

(f)

Ionics

match with the standard XRD data; the corresponding plane reflections have been assigned to the diffraction rings. Figure 4a, b shows the TEM images and the SAED diffraction pattern (inset) for the calcined samples prepared with and without sonication. Figure 4c, d shows the HRTEM images of the calcined samples prepared with (LFA) and without (LF) sonication. The TEM images of the sample prepared with sonication (LFA) show rod-like structures with large particle size when compared with the as-prepared samples. The inset of Fig. 4a shows the nanorod-like structure and the SAED pattern confirms the polycrystalline nature. The TEM

images of the sample prepared without sonication shows no specific morphology. The average crystallite size for the nanorods and nanoparticles is found to be 94 and 210 nm, respectively. The aspect ratio for the nanorods was calculated and found to be 2.8. From the HRTEM images, the lattice spacingd has been calculated and found to be 3.103 and 3.041 for LFA and LF, respectively, which represents the (111) plane with d value 3.231 for LaF3 in the hexagonal structure as confirmed from the XRD analysis. Figure 4e, f shows the SAED pattern of calcined LFA and LF, respectively. The SAED pattern confirms the polycrystalline nature of the prepared sample. The d spacing values have been

Fig. 4 TEM images of the calcined samples a with sonication and b without sonication. HRTEM images of the calcined samples c with sonication and d without sonication. SAED pattern of the calcined samples e with sonication and f without sonication

(a)

LFA

(b)

(c)

(d)

(e)

(f)

Ionics Fig. 5 EDAX spectra for lanthanum fluoride a nanorods and b nanoparticles

LFA

b
LF

La

Counts

La F La

Counts

La La La La F 10 5 La La

10

Energy (eV)

Energy (eV)

calculated and the results match with the standard XRD data; the corresponding plane reflections have been assigned for the diffraction rings.

Figure 5 shows the energy dispersive X-ray spectrum (EDAX) of the prepared lanthanum fluoride nanorods and nanoparticles. From the spectra, it is clear that there are no

250

b
LFA
200

LF
0.10
2 11 m /g

Quantity Absorbed (cm /g STP)

200

2 5m /g
0.08

LFA

Quantity Absorbed (cm /g STP)

0.10

LF

150
1/[Q(Po/P-1)]

1/[Q(Po/P-1)]

150

0.06

0.08

0.06

100

0.04

100

0.04

0.02

0.02

50
0.00 0.00 0.02 0.04 0.06 0.08 0.10

50
0.00 0.00 0.05 0.10 0.15 0.20 0.25

Relative Pressure (P/Po)

Relative Pressure (P/Po)

0 0.0 0.2 0.4 0.6 0.8 1.0

0 0.0 0.2 0.4 0.6 0.8 1.0

Relative Pressure (P/Po)

Relative Pressure (P/Po)

c
0.00035 0.00030

d
0.00035

BJH Desorption Dv (d)

LFA
0.00030 0.00025

BJH Desorption Dv (d)

LF

dV/dw (cm/g)

0.00025 0.00020 0.00015 0.00010 0.00005 0.00000 0 500 1000 1500 2000

dV/dw (cm/g)

0.00020 0.00015 0.00010 0.00005 0.00000 -0.00005 0 500 1000 1500 2000

Pore Width ()

Pore Width ()

Fig. 6 N2 adsorptiondesorption plots for lanthanum fluoride prepared a with sonication (LFA), b without sonication (LF), c BJH desorption plots for lanthanum fluoride prepared with sonication (LFA), and d without sonication (LF)

Ionics Fig. 7 Formation mechanisms of lanthanum fluoride nanorods and nanoparticles

La(NO 3)3

NH4F

La(NO3)3

NH4F

LaF3
Nucleation

Sonication

LaF3

Nucleation

Calcination

Calcination

impurity traces in the sample, which confirms the formation of lanthanum fluoride. Surface area analysis (BET) Physisorption measurements using BET (Brunauer EmmettTeller) method have been employed to determine the specific surface area and porosity of the prepared nanoparticles. Figure 6a, b shows the nitrogen adsorption desorption isotherms for the lanthanum fluoride nanoparticles prepared with (LFA) and without (LF) sonication. The inset of the figures shows the BET surface area plots of the prepared nanoparticles. All of the samples prepared show a similar trend of nitrogen adsorption and desorption isotherms, which is classified as type IV isotherm [20]. The initial part of the isotherm is attributed to monolayer multilayer adsorption. From the adsorptiondesorption isotherms, it is concluded that the surface has mesopores. The specific surface area of the prepared nanoparticles has been calculated from the plots and found to be 11 and 5 m2/g for the samples prepared without and with sonication, respectively. From the BET analysis, it is clear that the pore size decreases as the sonication time increases.

The isotherms exhibit a hysteresis loop, which is associated with capillary condensation taking place in mesopores and the limiting uptake over a range of high p/p0. The shapes of the hysteresis loops have often been identified with specific pore structures. The hysteresis loop is classified into four types, of which the present isotherm exhibits the type H3 loop, which does not exhibit any limiting adsorption at high p/p0, and is observed with aggregates of plate-like particles giving rise to slit-shaped pores [20]. The pore size distribution calculated by the Barnett JoynerHalenda (BJH) method for the samples confirms the presence of mesopores in the prepared samples. The BJH adsorption plots of lanthanum fluoride prepared with (LFA) and without (LF) sonication are shown in Fig. 6c, d. From the adsorption plots, the average pore diameter of the particles has been found to be distributed in the range 100200 nm. Formation mechanism of nanoparticles and nanorods Figure 7 depicts the formation mechanism of lanthanum fluoride nanorods and nanoparticles. When ammonium fluoride solution is added to the lanthanum nitrate solution drop by drop, the fluorine ions react with cerium ions to

Ionics

a
100000 90000 80000 70000 60000

b
40000

LF LFA 633 K

35000 30000 25000

LF LFA 663 K

Z"

Z"

50000 40000 30000

20000 15000 10000

20000 10000 0
0 10000 20000 30000 40000 50000 60000 70000 80000 90000100000

5000 0
0 5000 10000 15000 20000 25000 30000 35000 40000

Z'

Z'

c
20000 18000 16000 14000 12000

d
8000

LF LFA 693 K

7000 6000 5000

LF LFA 723 K

Z"

Z"
0 200 4000 6000 8000 10000 12000 14000 16000 18000 20000

10000 8000 6000

4000 3000 2000

4000 2000 0 1000 0

0 1000 2000 3000 4000 5000 6000 7000 8000

Z'

Z'

Fig. 8 ColeCole plot for the prepared lanthanum fluoride nanorods (LFA) and nanoparticles (LF) at a 633 K, b 663 K, c 693 K, and d 723 K

form lanthanum fluoride in hexagonal structure, which is the structure of lanthanum fluoride as confirmed from the XRD analysis. The TEM images show that some particles were found to be in hexagonal shape; however, most of the particles were in irregular shape. The reason for the deviation from the expected hexagonal structure may due to the preparation of the sample without any external driving force/structure directing force like sonication energy. When the particles are prepared under sonication, the particle grow in hexagonal/elongated hexagonal shape, but due to the cavitational effect caused by sonication the edges of the elongated hexagon are curved to give a rod-like structure which is the deformed shape (edges) of an elongated hexagon. It is clearly visible that there an

additional number of particles were rod-like in shape when the solution was sonicated. The shape formation is credited to the effect of sonication. As the prepared nanoparticles were calcinated at 350 C (without sonication) and 300 C (with sonication), the nanoparticles/nanorods get agglomerated to form large-sized particles. The size of the particle gets increased considerably, which is confirmed from the TEM analysis. It is interesting to note that the particles prepared under sonication, when calcinated, show the same morphology of nanorods and the particles prepared without sonication show no distinct structure similar to the as-prepared sample. Hence, it can be concluded that sonication has greatly influenced the morphology of LaF3.

Ionics Fig. 9 Conductance spectra of the prepared lanthanum fluoride: a nanorods (LFA) and b nanoparticles (LF)
-1

-3.5

-3.5

a
-4.0
-1

b
-4.0

Scm

-4.5

Scm Log

-4.5

Log

-5.0 LFA 633 K 663 K 693 K 723 K 2 3 4 5 6 7

-5.0 LF 633 K 663 K 693 K 723 K 2 3 4 5 6 7

-5.5

-5.5

-6.0

-6.0

Log

Hz

Log

Hz

Impedance spectra analysis Figure 8ad shows the Cole-Cole plot for the prepared Lanthanum fluoride nanorods and nanoparticles at 633, 663, 693, and 723 K, respectively. The impedance spectra show a semicircle in the high frequency region attributed to the grain interior resistance. The appearance of the high frequency semicircle is due to the parallel combination of bulk resistance and bulk capacitance of the samples. The bulk capacitance and bulk resistance values have been extracted using Equivalent circuit program [21]. The bulk capacitance values are calculated using the relation: wmax RC 1 4

The ionic conductivity is calculated using the relation: s l RA resistance of the material thickness of the pellet (cm) area of the pellet (cm2) 5

R l A

The thus calculated bulk capacitance values are found to be in the order of Pico farad (pF), which indicates the nature as grain interior resistance. The grain interior resistance is contributed by the motion of F ions along the grains and is known as the bulk resistance of the material [10]. The center of the semicircle falls below the real axis, indicating the nondebye nature of the material. The impedance plot also shows the characteristic capacitive spike which may be attributed to the effect of blocking electrodes. As expected at higher temperatures, the bulk resistance decreases and the diameter of the semicircles associated with them decreases, leaving only the capacitive blocking spike observable over the measured frequency range [22]. According to Hoff et al. and Maximov et al. [23, 24], fluoride anions occupy different positions of the sublattice proportionally in the lanthanum fluoride crystal. The mobility of fluoride ions varies with the positions that they occupy. At low temperature, most of the fluoride ions are difficult to move; the conductivity is contributed by a small amount of highly free fluoride ions and hence the resulting low ionic conductivity. As the temperature increases, more and more fluoride ions turn to occupy the high-mobility sublattice positions, resulting in high conductivity, and this takes place from 573 K for the nanorods (LFA) and from 633 K for the nanoparticles (LF) in the present study.

The maximum conductivity value at 723 K for the nanorods (LFA) was found to be 1.4104 S cm1 and for the nanoparticles (LF) 6.2105 S cm1. The increase in ionic conductivity with increase in sonication time can be attributed to the effect of sonication. During sonication, pores are generated on the surface of the nanoparticles due to the collapse of hot bubbles over the surface, which in turn reduces the particle/pore size. The particle size was found to decrease for the sample prepared with sonication and the surface area was calculated using BET analysis. It is found to decrease for the sample prepared with sonication. The pore size plays a vital role
-0.8 -1.0 -1.2

LF LFA

Log T (Scm K)

-1.4 -1.6 -1.8 -2.0 -2.2 -2.4 -2.6

1.35 1.40 1.45 1.50 1.55 1.60

-1

1000/T (K -1 )

Fig. 10 Temperature-dependent conductivity of the prepared lanthanum fluoride nanorods (LFA) and nanoparticles (LF)

Ionics

in ionic conductivity and, as observed from the BET plot, the decrease in pore size for the sample prepared with sonication, hence the increase in conductivity for the sample prepared with sonication (LFA) than that prepared without sonication (LF). Conductance spectra analysis Figure 9 shows the conductance spectra for LaF3 nanorods and nanoparticles at different temperatures. The conductance spectra shows two distinct regions: the low frequency plateau, which indicates the dc conductivity of the material, and the high frequency dispersion region, which obeys the power law feature () n. The material was found to obey Jonshers Universal Power Law [25] given as: sw s dc Awn 6

Conclusion Lanthanum fluoride nanorods and nanoparticles have been prepared by a simple chemical method with and without ultra sonication. The TG/DTA analysis presents the formation of lanthanum fluoride nanorods at around 230 C and nanoparticles at around 290 C, which is attributed to the influence of sonication. Nanostructural analysis shows the formation of nanorods. BET analysis confirms the presence of mesopores. The surface area was found to decrease for the nanorods. The maximum ionic conductivity value at 723 K for the nanorods was found to be 1.4104 S cm1 and for the nanoparticles 6.2105 S cm1, which implies that the ionic conductivity increases when the morphology changes. Temperaturedependent conductivity shows the Arrhenius-type thermally activated process in the sample.

The conductance spectra were fitted using Jonshers Power Law and the value of n was extracted; it was found to be less than one, which indicates the translational motion of the fluorine ions in the material. From the plot, it is clear that as the temperature is increased the DC plateau region shifts towards the high frequency region, indicating increase in mobile charge carriers [26]. According to jump relaxation model, at low frequencies, an ion jumps from one site to its neighboring vacant site, successfully contributing to dc conductivity. The observed conductivity relaxation at high frequencies can be due to the probability of the correlated forwardbackward hopping together with the relaxation of the ions. From the results, it had been found that the dc ionic conductivity values are in good agreement with the bulk conductivity values obtained from the impedance plot. Temperature-dependent conductivity Figure 10 shows the variation of conductivity with respect to reciprocal of temperature for the lanthanum fluoride nanoparticles and nanorods. The linear variation of log T Vs 1,000/T plot suggests an Arrhenius-type thermally activated process. The conductivity is expressed as sT s 0 eEa =kT where 0 Ea pre-exponential factor activation energy 7

Acknowledgement The authors wish to thank Prof. B.A. Boukamp and Prof. Issac Abrahams for providing software for impedance data analysis. One of the authors, D. Arun Kumar, acknowledges DRDOBU Center for Life Sciences, Bharathiar University, Coimbatore, for providing Senior Research Fellowship.

References
1. Fergus JW (1997) Sens Actuators B Chem 42(2):119130 2. Schoonman J, Oversluizen G, Wapenaar KED (1980) Solid State Ionics 1:211221 3. Miura N, Hisamoto J, Yamazoe N, Kuwata S (1988) Appl Surf Sci 33/34:12531259 4. Lilly AC Jr, LaRoy BC, Tiller CO, Bruce Whiting (1973) J Electrochem Soc 120:16731676 5. Szeponik J, Moritz W (1990) Sens Actuators B Chem 2(4):243 246 6. Moritz W, Mller L (1991) Analyst 116:589595 7. Komljenovic J, Krka S, Radic N (1986) Anal Chem 58:2893 2895 8. Wu XJ, Su F, Qin XY (1993) Mater Res Soc Symp Proc 286:27 30 9. Puin W, Rodewalld S, Ramlau R, Heitjans P, Maier J (2000) Solid State Ionics 131:159164 10. Vijayakumar M, Selvasekarapandian S, Gnanasekaran T, Fujihara S, Koji S (2004) J Fluor Chem 125(1):11191125 11. Feng WY, Wen TY, Shan HY (2004) Trans Nonferr Met Soc China 14(4):378381 12. Fang ZJ, Shen WZ, Jun ZZ, Min LW, Xin DH (2001) Wear 249:333337 13. Xun W, Jing Z, Qing P, Dong LY (2005) Nature 437:121124 14. Liu Y, Zhao Y, Yu L, Wu Z (2009) J Alloys Compd 485:L1L4 15. Suslick KS (1988) Ultrasound: its chemical, physical, and biological effects. VCH Verlagsgesellschaft, Weinheim, Germany 16. Suslick KS, Choe SB, Cichowlas AA, Grinstaff MW (1991) Nature 353:414416 17. Wu DX, Wu XJ, Lu YF, Wang H (2006) Trans Non Ferr Met Soc China 16:828832

The activation energy was calculated from the slope of the Arrhenius plot and found to be 0.48 and 0.52 eV for nanorods and nanoparticles, respectively.

Ionics 18. Arun Kumar D, Selvasekarapandian S, Nithya H, Sakunthala A, Hema M (2010) Physica B 405:38033807 19. Cullity BD (1956) Elements of X-ray diffraction. Wesley, Reading 20. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Pure Appl Chem 57 (4):603 21. Boukamp BA (1986) Solid State Ionics 18 & 19 136140 22. Selvasekarapandian S, Vijayakumar M (2003) Mater Chem Phys 80:2933 23. Hoff C, Wiemhfer HD, Glumov O, Murin IV (1997) Solid State Ionics 101:445449 24. Maximov B, Schulz H (1958) Acta Crystallagraphica B 41:8891 25. Jonscher AK (1977) Nature 267:673678 26. Kawamura J, Sato R, Mishna S, Shimoji M (1987) Solid State Ionics 25:155164