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Carbon – Sci. Tech. 5/1 (2013) 225 – 230
Carbon – Science and Technology
ISSN 0974 – 0546 http://www.applied-science-innovations.com
ARTICLE Received : 15/06/2013, Accepted : 12/08/2013 ------------------------------------------------------------------------------------------------------------------------------
Special Section on Advanced (Non-Carbon) Materials Effect of Temperature on Crystallite Size of Lanthanum Cerium Oxide (La2Ce2O7) and its Optical Properties
Hozefa Tinwala (A, *), D. C. Shah (A) and Jyoti Menghani (B) (A) Department of Applied Physics, Sardar Vallabhbhai National Institute of Technology, Surat 395007, India. (B) Department of Mechanical Engineering, Sardar Vallabhbhai National Institute of Technology, Surat - 395007, India. *Corresponding Author : Hozefa Tinwala, Tel: +91-8469691252. The effect of the calcination process on the crystallite size and optical properties of Lanthanum Cerium Oxide (La2Ce2O7) nanopowders synthesized using co-precipitation process were reported. X-ray diffraction analysis revealed that the synthesized nanopowders calcined at various temperatures have cubic fluorite phase. Thermal Gravimetric Analysis (TGA), X-ray Diffraction (XRD), Energy Dispersive Spectroscopy (EDS), Transmission Electron Microscopy (TEM), Laser Raman Spectroscopy, and UVvisible spectroscopy were utilized to characterize phase structure and morphology of the products. Keywords : Crystallite Size, Co-precipitation Method, Thermal Properties, Optical Properties, Structural Properties. -----------------------------------------------------------------------------------------------------------------------------Introduction : Rare earth doped ceria (REC) pressing and sintering , conventional cowith a fluorite structure is used in wide precipitation method, . Some of these applications such as solid oxide fuel cells (SOFC) methods are multistep , costly , and due to its higher oxygen conductivity than that of produces particles greater than nano-size [13, 14]. ZrO2 solid solution [1, 2, 3] and thermal barrier Long heating time is essential for solid state coatings [4, 5] due to its properties such as high method, and cold pressing method, but results in melting point, low thermal conductivity, thermal formation of micron sized particles. In expansion match with metallic substrate, no phase hydrothermal and conventional co-precipitation transformation between room temperature and method, water is used as solvent for the synthesis operation temperature, chemical stability, good of La2Ce2O7, since water is used externally, adherence to the metallic substrates and low results in the formation of hard agglomerates, due to hydrogen bonding. Thus by the elimination use sintering rate of the porous microstructure [6, 7]. Recent work done for the preparation of La2Ce2O7 of additional water, we can eliminate the include the work by Benjaram et al. , formation of agglomerate . Andrievskaya et al. , Cao et al. , Wang et al. , Different methods were used in the Preparation of lanthanum cerium oxide preparation of La2Ce2O7, such as hydrothermal nanopowders and studying its thermal and optical method [11, 12], solid state method , cold properties is a new research subject, practical 225
4 M for triethylamine solution. Mechanical Engineering Department.6H2O and (C2H5)3N were dissolved into the solvent separately. and solution was filtered by a suction filter using Whatman 42 (pore diameter 2.© Applied Science Innovations Pvt. Precipitates was washed with solvent alcohol many times. unreacted trithylamine. Raman Spectroscopy.1 M mixture of cerium nitrate and lanthanum nitrate solution was mixed in a flask and titrated using 100 ml of 0. and UV-visible spectroscopy. and calcined at different temperatures for 3 hours . Bruker X-ray diffractometer (D2 Phaser)). uniformity. Transmission Electron Microscopy (TEM). Very few techniques have been proposed to synthesize nano-sized lanthanum cerium oxide (La2Ce2O7) with promising control of properties. India methods are still needed for synthesizing high quality ultrafine powders with required characteristics in terms of their size. The cerium nitrate hexahydrate Ce(NO3)3·6H2O (Spectrochem 99%) and lanthanum nitrate hexahydrate La(NO3)3. 5/1 (2013) 225 – 230 precipitates was dried for 24 hours. at SIC.1 M for mixture of cerium nitrate and lanthanum nitrate solution and 0. La(NO3)3. Transmission electron microscopy (TEM. Thermogravimetric analysis (TGA. Laser Raman Spectroscopy. SVNIT. Philips Tecnai 20. TGA Analysis was done using RIGAKU TGA701. Triethylamine (C2H5)3N and ethanol were used as precipitant and solvent respectively. The stirring was continued till the solution of cerium nitrate and lanthanum nitrate were empty. Results and Discussion : Thermal Gravimetric Analysis (TGA) : Figure (1) : Graph showing the weight loss of sample with respect to increment in temperature Figure (2) : Graph showing the weight loss of sample with respect to increment in temperature. TGA-701. Rikagu. Japan).6H2O (Loba Chemie 99 %) were used as source for synthesizing lanthanum cerium oxide La2Ce2O7 powder. Figure (1a) shows the graph of weight loss vs temperature. then again washed with acetone to remove the remaining alcohol. In the present study we report the effect of the calcination process on the crystallite size and optical properties of Lanthanum Cerium Oxide (La2Ce2O7) nanopowders synthesized using coprecipitation process using Thermal Gravimetric Analysis (TGA). morphology. Energy Dispersive Spectroscopy (EDS). Experimental Method : The co-precipitation process for making lanthanum cerium oxide La2Ce2O7 was followed according to the work reported by Li et al . Electron dispersive spectroscopy (EDS). The whole precipitation process was performed at room temperature..5 µm) filter paper. Ltd. specific surface area and crystallinity. 0. X-ray Diffraction (XRD). The ﬁnal concentrations were 0. and UV-visible spectroscopy were used as analytical tools to characterize the as prepared powder. Ce(NO3)3·6H2O.4 M triethylamine precipitant solution kept in another flask under mild stirring. and other byproduct. X-ray diffraction (XRD. Tech. Holland). In this graph the weight of . Then the 226 Carbon – Sci.
95 planes which are typical of face-centered cubic fluorite structure of CeO2 . Figure (3) shows the XRD patterns of Lanthanum Cerium Oxide (La2Ce2O7) Element Weight % Atomic % nanopowders calcined at different temperatures.97 corresponding to (1 1 1). (2 0 0). where Dhkl is the crystal size perpendicular to crystal face (h k l).) were observed. X-Ray Diffraction (XRD) Analysis : Bragg showed in 1913 that diffraction from a crystal is described by the equation now known as Bragg's law : 2 d(hkl) sinθ = nλ (1) Carbon – Sci. where n is the order. Figure (4) : Crystallite Size vs Temperature graph of Nanopowders Detailed analysis indicates that XRD pattern match well with the standard cubic fluorite phase of CeO2. θ is onehalf of the diffraction angle. This feature can be attributed to the formation of La2Ce2O7 solid solution Figure (3) : XRD pattern for Naopowder Calcined at 600ºC.66 17. D hkl = κλ β cos θ .5406 Å and β is full width half maximum of the peak at (1 1 1) plane. Furthermore. A powder pattern therefore contains a set of diffraction peaks at 2θ positions that correspond to the interplanar spacings in the crystal . India the substance decreases up to around 500 ºC. but after that there is zero or negligible weight loss. 750ºC. no peaks corresponding to the individual oxides (La2O3. at K C Pattel Oxide (La2Ce2O7) as observed from EDS is show Research and Development Center. Charotar in the table below : University of Science and Technology Table (1) : Compositon of La2Ce2O7 sample (CHARUSAT).08 All the samples exhibit typical peaks La 41. λ is 1. (3 1 1) Ce 41.98 64. Energy Dispersive Spectroscopy (EDS) : XRD Analysis was done using Bruker X-ray Elemental composition of Lanthanum Cerium diffractometer (D2 Phaser).36 17. K is constant. 5/1 (2013) 225 – 230 sizes were estimated from the line broadening of the peak at (1 1 1) plane using Debye Scherrer equation . Ltd. Tech. (2) This equation allows one to measure the perpendicular distance (dhkl) between imaginary planes which form parallel families and which intersect the repeating unit cell filled with atoms in a way described by the Miller indices (hkl). O 16. (2 2 0). No evidence of La2Ce2O7 pyrochlore phase (Fd3m) could be found.. 900ºC and 1050ºC.© Applied Science Innovations Pvt. Which suggest that all the volatile material is removed around that temperature. The crystallite 227 . The crystallite size increased with increasing calcinations temperature. X rays of wavelength λ may be thought of as reflecting from these imaginary planes at the measurable angle θ.
In above spectra two broad peaks are observed. EDS measurements carried out on the as-prepared La2Ce2O7 nanopowders indicates.. The particles appear to posses the particle size 55 to 80 nm with cubic shape.© Applied Science Innovations Pvt. This shifting is due to change in the MO vibration frequency after incorporation of La in 228 Figure (6) : TEM Image of Sample . The 1st peak is CeO2 peak it is shifted from 464. 5/1 (2013) 225 – 230 Figure (5) : EDS graph of sample EDS measurements were carried out at M. Transmission Electron Microscopy (TEM) : TEM analysis was done using Philips Tecnai 20. the chemical composition of La2Ce2O7 is closing to the stoichiometric composition of La2Ce2O7. wich has F2g symmetry and can be viewed as a symmetric breathing mode of the O atoms around each cation. particle size and structure of the synthesized La2Ce2O7 were illustrated by TEM. Figure (3a) and (b) illustrate the TEM images of the La2Ce2O7 nanocrystals calcined at 900ºC. Cubic fluorite structure metal dioxides have only a single allowed Raman mode. Baroda. University. Ltd.5 nm. The morphology. Vallabh vidya nagar. Figure (7) : TEM Image of Sample Laser Raman Spectroscopic Analysis : Figure (8) : Laser Raman Spectroscopic graph of Nanopowder Calcined at 900ºC. The exposure time was 50 sec and the wavelength of laser source was 514. Ramnor HG-2S Spectrometer. Laser Raman Spectroscopic Analysis was done using Ar-Laser. at SICART. at IIT Bombay. Tech. 4W power (all lines). India Carbon – Sci. 1st peak is at 451 frequency and 2nd peak is at 570 cm-1.5 cm-1 to 451 cm-1.S. Anand.
B.  W. Bae. Arai. Ma. Tuller.© Applied Science Innovations Pvt. Electron Diffraction Spectroscopy (EDS) confirms L2Ce2O7 phase. From X-ray diffraction (XRD) Analysis of sample Calcined at 600ºC.  K. 23]. W. Ceram. hν. Gong. As observed from the UV-Visible graph.3 as the calcination temperature increases. J. B. Xu. J. SVNIT. Nowick. . S. Lee. S. Tech. 200 (2006) 5113-18. This method is found to be simple and economical for the preparation of La2Ce2O7 nanoparticles. Solid State Ionics 52 (1992) 165-72. I0 is the intensity of light after refrence glass plate. Jang. UV-visibile Spectroscopic Analysis : Carbon – Sci. and is due to the effect of dopant. 5/1 (2013) 225 – 230 Conclusions : La2Ce2O7 nanocrystals were produced via co-precipitation method. 229 . A. The Thermal Cycling Behavior of Lanthanum–Cerium Oxide Thermal Barrier Coating Prepared by EB–PVD. H. which account for the difference in the ionic radius [21. S. S. Laser Raman Spectroscopy reveal the presence of vacant spaces due to doping of Lanthanum. Q. particle size and structure of the synthesized La2Ce2O7 was observed. Kwak. From Transmission Electron Microscope (TEM) morphology. K. C.  K. Y. . 900ºC and 1050ºC standard cubic fluorite phase of Lanthanum Cerium Oxide (La2Ce2O7) is observed. B. M. respectively. Inoue. K. I is the transmitted intensity of light after placing powder film. L. Doped Ceria as a Solid Oxide Electrolyte. Laser Raman Spectroscopy reveals an extra peak at 570 nm. Here Absorption Coefficient α was calculated using the following equation : α= 1 I ( ) I0 d (3) where d is path length or thikness of powder film. Ltd. Soc. India CeO2. Vibrations are rapid for contracted lattice and slow down for expanded lattice so that band shifts to higher and lower wavenumbers. Shim. Coat. S. Formation and thermal properties of fluorite-pyrochlore composite structure in Figure (9) : Plot of (αhv)2 vs hv for 750ºC and 900ºC. T. H. 22. References :  H. Setoguchi.. The peak at 570 cm-1 is the new feature. Lee. Kim. Electrochem. the bandgap of the synthesized material varies from 2. Soc. and TGA of sample Calcined at 750ºC also shows that the weight loss is negligible. Surf. H. Due to doping the O vacancies increases. UV-Visible spectroscopy is frequently employed for band gap calculation. Cao. The nanoparticles have size in range 5580 nm. H. H. UV-Visible spectropic Analysis was done at Applied Physics Department.0 to 2. T. X. S. Choo. 122 (1975) 255-259. The crystal structure of ionic conductor LaxCe1−xO2−x/2.  J. 750ºC. Eguchi.. K. XRD and TEM results suggest that the nanoparticles are cubic fluorite in structure. Thermo gravimetric analysis (TGA) of Nanoparticles in hydroxide form shows that weight loss is negligible as temperature increases above 500ºC. T. 24 (2004) 1291–94. Electrical properties of ceria-based oxides and their application to solid oxide fuel cells. Kim. Oh. And from UVvisible Spectroscopy it is observed that there is change in bandgap with increase in calcinations temperature. The products are cubic fluorite in structure. Eur. Technol. C. The band gap energy (Eg) is obtained from the intercept of the straight plot of (αhν)2 vs.
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