Journal

J. Am. Ceram. Soc., 97 [3] 718724 (2014) DOI: 10.1111/jace.12741 2013 The American Ceramic Society

Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method
Debadutta Prusty, Abhishek Pathak, Apparao Chintha, Bratindranath Mukherjee, and Anirban Chowdhury,,

Research & Development, Tata Steel Limited, Jamshedpur 831001, India

Materials Research Centre, Indian Institute of Science, Bangalore 560012, India Researchers have used this as a host material for immobilization of actinides8 as well. It has also been reported to be an eective buer layer for yttrium barium copper oxide (YBCO)-coated conductors to prevent metal ion diusion into the YBCO layer.9 Previous research on this material reveals its utility in gaining insight into the transport properties of electrodes as it has been found to have formed at the electrode/YSZ interfaces in LaCoO3 and LaMnO3 cathodes.10,11 The traditional solid-state method for producing La2Zr2O7 includes several hours of grinding of La2O3 and ZrO2 powders followed by compaction and sintering of the mixture, which requires a very high temperature and long sintering time.12,13This reaction often yields extensively agglomerated products and an unreacted core as diusion has to occur through the product layer. Also, due to high temperature, grain growth occurs which limits the performance of the product. To alleviate these problems, the focus has been changed to wet chemical methods which ensure mixing occurs at the molecular level. Several methods such as hydrothermal synthesis,14 hydrazine method,15 solgel technique,16 and coprecipitation1719 have been employed to obtain La2Zr2O7. Nair et al.18 synthesized La2Zr2O7 using precursors La(NO3)36H2O, ZrO(NO3)2xH2O, and ZrOCl28H2O by three dierent techniques, namely, citrate method, ash combustion method using urea as the fuel, and coprecipitation method. The results of coprecipitation method were found to be more reproducible than those of the other two processes. In coprecipitation, the reaction rate can easily be controlled by controlling the pH, stirring rate, and washing procedure. This work investigates the phase evolution in lanthanum zirconate prepared by coprecipitation method and sheds light on compositional anomalies that occurred due to introduction of an extra step of ultrasonication while collecting the precipitate from the solution. The phase evolution has been studied by X-ray diraction (XRD), dierential scanning calorimetry (DSC) as well as transmission electron microscopy (TEM).

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X-ray diraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations conrmed the depletion of La3+ ions in the system. Analysis using Vegards law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La2Zr2O7. Noteworthy is also the dierence between crystal sizes in the samples prepared by with and without ultrasonication step. This dierence has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The dierential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La2Zr2O7 is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.

I.

Introduction

HERMAL barrier coatings, owing to their excellent thermal stability and resistance to corrosive gases, are used to provide protection to metallic parts at higher temperatures in aircraft gas turbines1,2 as well as in blast-furnace tuyeres3 in steel industries. Typically, a thermal barrier coating is composed of two layers, namely, a bond coat, which is normally made of NiCrAlY alloy, and a ceramic top coat. Of all the materials, yttria-stabilized zirconia (YSZ) is the most widely used material for the top coat. But due to its oxygen transparency, rapid high-temperature oxidation of the bond coat occurs, giving rise to a thick thermally grown oxide layer. This causes failure by spallation of the YSZ top coat.4 YSZ also undergoes phase transformation at higher temperatures, which results in formation of cracks, leading to delamination of the coating.5 Over the past few years, these concerns have stimulated interest in developing suitable alternative ceramic compositions for barrier coatings. Among these materials, one interesting candidate is lanthanum zirconate (La2Zr2O7) which has lower thermal conductivity and lower sinterability compared to YSZ.4 La2Zr2O7 along with its ruthenium- and platinum-doped derivatives has also been investigated as a catalyst in dry reforming of methane.6,7

II.

Experimental Procedure

T. Vanderahcontributing editor

Manuscript No. 33601. Received August 3, 2013; approved November 1, 2013. Present address: Department of Materials Science and Engineering, Indian Institute of Technology Patna, Patliputra Colony, Bihar 800013, India Author to whom correspondence should be addressed. e-mail: anirban.chowdhury@ gmail.com

For the synthesis of lanthanum zirconate, the selected precursors were lanthanum nitrate (La(NO3)36H2O, 99.9% pure; Alfa Aesar, Lancashire, UK) and zirconyl oxychloride (ZrOCl28H2O, 98% pure; LobaChemie, Mumbai, India). The process steps are shown in the Fig. 1. The precipitates were collected at pHs 911. The samples corresponding to the precipitates collected at pHs 9, 10, and 11 are referred to as LZ-9, LZ-10, and LZ-11, respectively. Thermal analysis of dried precipitates as well as precursors was performed in air using a dierential scanning calorimeter (STA 449 F3Jupiter NETZSCH, Selb, Germany) from room temperature to 1500C at a heating rate of 10C/min. As will be explained in the following section, pH 11 was found to be the optimum pH for yielding lanthanum zirconate. The sam-

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Fig. 1.

Schematic ow chart for preparation of lanthanum zirconate by coprecipitation.

ple collected at pH 11 was calcined in air at 900C. However, after thoroughly analyzing the XRD pattern of the calcined sample, a signicant shift of the peaks with respect to the standard JCPDS pattern was observed. With the aim of resolving this issue, an additional step of ultrasonication between two centrifugation cycles was introduced. Ultrasonication is an eective technique to disperse small particles in solutions.20 It involves creation of small vacuum bubbles during rarefaction and their collapse during compression cycle of the sound wave which breaks the agglomerates resulting in compositional homogenization. The sample collected from the solution with a pH value of 11 without ultrasonication after each centrifugation step was designated as A and the one with ultrasonication as B. Both the samples were calcined at 900C. Powder XRD was performed on the samples using a diractometer (PANalyticalXPert Pro, Almelo, the Netharlands) with monochromatic CuKa radiation to study their phase evolution with temperature. Continuous scans were performed over an angular range of 1090 (2h). The collected patterns were analyzed on PANalyticalXPert High Score software. The microstructure and surface morphology of the samples were obtained using a scanning electron microscope (SEM, SUPRA 25; ZEISS FEG, Oberkochen, Germany). The energy used for analysis was 10 kV. High-resolution transmission electron microscopy (HRTEM, Hillsboro, OR) studies were carried out using a Tecnai 320 W-lament transmission electron microscope operated at 200 kV.

III.

Results

The DSC plots of the dried samples LZ-9, LZ-10, and LZ-11 are shown in Fig. 2(a). The endothermic peak near 80C, present in the samples LZ-9 and 10, is due to evaporation of

physically adsorbed water. Two small endothermic peaks at 334C and 350C in LZ-10 and LZ-11, respectively, might be due to hydroxide decomposition.18 The exothermic peaks in the range of 820C880C depict the crystallization of LZ; this is also corroborated by the XRD patterns. To study these endothermic peaks in detail, we carry out the dierential scanning calorimetric analysis of precursors. Figure 2(b) depicts the DSC plots of the precursors. In case of La(NO3)36H2O, several endothermic peaks are observed between room temperature and 650C. The thermal decomposition behavior of hydrous lanthanum nitrate in air was studied by Gobichon et al.21 by means of thermogravimetric analysis and temperature-dependent XRD. According to their work, the dehydration proceeded via formation of several lower hydrates over the temperature range 50C200C and nally La(NO3)3 was obtained at around 245C. The anhydrous nitrate in turn produces lanthanum oxynitrate (LaONO3) which reacts with atmospheric carbon dioxide to yield monoclinic lanthanum dioxycarbonate (La2O2CO3). These reactions occur in the temperature range 400C 480C. This phase transforms into a hexagonal phase with partial decomposition into La2O3 and nally, the oxide phase La2O3 is obtained from this hexagonal phase near 650C. The peak positions in DSC are close to those of mass loss processes in the thermogravimetric analysis experiment carried out by the above-mentioned authors. Therefore, we believe the endothermic peaks in the region 50C220C correspond to the loss of water of crystallization and 400C 600C to the formation and decomposition of the oxynitrate and the dioxycarbonate. For ZrOCl28H2O, the peaks below 100C are indicative of loss of water of crystallization. The strong endothermic peak at 152C is probably due to the decomposition of ZrOCl2 to some hydrated Zr oxides. A sharp endothermic peak is observed at 1348C for LZ-9; similar evidence with a much lower intensity is observed in LZ-10 sample as well. We are unsure about the

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Fig. 2. Dierential scanning calorimetry heating curves of (a) the precipitates (dried at 110C) collected at pHs 9 (LZ-9), 10 (LZ-10), 11 (LZ-11) (b) the precursors.

origin of the peak at 1348C; however, believe it to be due to a phenomenon similar to decomposition and/or secondary phase melting. Literature reports suggest that the decomposition of LaOCl into La2O3 and LaCl3 is highly favorable and the decomposition temperature has been reported to be 934C.22 Also, the melting point of pure LaCl3 is 858C and it is in liquid form till 1740C.23 Nair et al.18 have not observed any endothermic peak when they had performed the dierential thermal analysis of powder precursor pre-

pared by coprecipitating La(NO3)36H2O and ZrOCl28H2O at pH 10 up to 1000C. As there is no evidence of endothermic peak in the range 50C1500C in LZ-11, we have selected 11 as the optimum pH to yield lanthanum zirconate powders and hence perform all the characterization on this sample. To date, there is lack of consistency in the selection of proper JCPDS les for indexing La2Zr2O7 system. Kong et al.24 indexed the uorite La2Zr2O7 pattern on the basis of

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JCPDS le no. 01-080-0471 which actually corresponds to Gd2Zr2O7 and depicts its maximum intensity peak at 29.37 (2h). Also, there have been published reports on La2Zr2O7 where the XRD patterns were suitably indexed without quoting the standard reference les used for the purpose.17,18 La2Zr2O7 primarily exists in two crystal structures; pyrochlore and uorite.25 We could nd only a calculated pattern (JCPDS le no. 01-075-0346) for uorite. The existence of (111), (331), and (511) peaks at 14.25, 36.34, and 43.58 2h, respectively (JCPDS le no. 17-450), is the signature of the pyrochlore phase. In this study, we have not observed any signicant contribution arising from these peaks. Hence, we have indexed the patterns obtained in this study with respect to the calculated le for uorite structure (JCPDS le no. 01-075-0346). The XRD patterns of samples A (processed without ultrasonication) and B (processed with ultrasonication) calcined at 900C are shown in Fig. 3. The peak positions, intensity ratios, and interplanar distances of the corresponding planes are listed in Table I. The extra peaks in sample B have not been listed for the ease of comparison. There are two signicant changes observed in the XRD patterns of samples A and B. One of them is peak shifting. It is to be noted that the peaks of sample A are shifted in position toward higher angles although the intensities are in well accord with the values reported in the JCPDS le 01-075-0346. As expected, this deviation increases as we move toward higher angles.

Fig. 3. X-ray diraction patterns of the samples processed without ultrasonication (sample A) and with ultrasonication (sample B); the * sign corresponds to extra peaks in sample B. The inset gure depicts the extent of peak broadening and shift for the (111) peak in the two samples. The patterns have been matched against the standard pattern of uorite (JCPDS le no. 01-075-0346).

Some extra peaks are also noticed in sample B although their intensities are very small as compared to those of major peaks. These extra peaks could be suitably matched up with LaOCl (JCPDS le no. 8-0477). The second signicant change is the dierence in the peak broadenings and intensities in the samples. As depicted in Table I, there is a large (~200%) increase in all of the full width at half maximums of the main peaks in sample A compared to sample B. Such broadenings can arise due to a number of factors such as crystallite size, microstrain, and concentration gradients in nonstoichiometric compounds.26 We have conrmed this evidence of peak shifts and broadening in sample A through repeated trials. However, the intensity of the extra peaks for LaOCl varied for both the samples (A and B).The crystallite sizes of A and B, calculated using Scherrers formula, were found out to be 18 and 45 nm, respectively. The scanning electron micrographs of sample A and sample B are shown in Figs. 4(a) and (b). The particle size in A is in the range of 40 10 nm while that in B is 120 30 nm. The dierence in the crystallite sizes of the samples is in well agreement with the XRD results; the TEM results also depicted a similar trend. Figures 5(a) and (b) show the HRTEM images collected from sample A and sample B, respectively. The fringe widths  for sample A of the shown planes are 3.0818 0.0066 A  and 3.2985 0.0145 A for sample B. The observed d spacing  in sample A matches reasonably well (3.0818 0.0066 A)  with the experimental data obtained from XRD (3.06 A). The d spacing obtained for sample B [Fig. 5(b)] is close to  of the pyrochlore (JCPDS le that of (311) plane (3.2521 A) no. 01-071-2363). Apart from the uorite reections in sample B, we also observe crystals with d spacings  3.4590 0.0224 A)  matching closely (3.5398 0.0398 A,  and (002) (3.441 A)  planes of with those of (101) (3.54 A) LaOCl. This is consistent with our XRD results as the extra peaks were attributed to LaOCl. Also detected was a crystal  This is in well accord with a d spacing of 5.0145 0.122 A.  of the (001) plane of monoclinic with the d value (5.087 A) ZrO2 (JCPDS le no. 37-1484). Although in XRD, no evidence of existence of pyrochlore and monoclinic ZrO2 phases in sample B was found, the HRTEM results hint at their presence in the sample. This may be due to the fact that XRD provides information about the bulk composition and is unable to detect phases that are present in very small amounts as the intensities of their peaks may get suppressed by the background intensity as well as the intensity of the major phase if their positions are close to those of major phase reections.27 The selected-area electron-diraction (SAED) patterns of samples A and B are shown in Fig. 6. In case of sample A, rings consisting of spots of uniform size could be observed. The calculated d spacings corresponding to the shown rings  for the rst four planes) (2.7521, 1.9729, 1.6345, 1.2373 A resemble those of (111), (200), (220), and (311) planes of the uorite phase. However, in sample B, there are spots of dif-

Table I.

Detailed Peak Lists for Samples A and B with Respect to Fluorite La2Zr2O7 Structure (JCPDS le no. 01-075-0346)
Sample B with ultrasonication 2h ()  d (A) I (%) FWHM () La2Zr2O7 (JCPDS le no 01-075-0346) 2 h ( )  d (A) I (%)  d (A)

Sample A without ultrasonication 2h () I (%) FWHM ()

29.160 33.803 48.658 57.624 60.481 71.329 78.747 81.201

3.0600 2.6496 1.8697 1.5984 1.5295 1.3212 1.2143 1.1837

100 26.06 32.89 21.64 4.27 2.64 5.17 3.74

0.4400 0.4557 0.6096 0.6485

28.683 33.237 47.730 56.623 59.415 69.778 77.102 79.514

3.1098 2.6934 1.9039 1.6242 1.5544 1.3467 1.2360 1.2045

100 28.79 39.17 27.60 4.86 2.92 5.74 4.10

0.1782 0.1942 0.2589 0.2926

28.571 33.109 47.525 56.393 59.143 69.480 76.776 79.154

3.1217 2.7035 1.9117 1.6303 1.5609 1.3518 1.2405 1.2090

100 26.2 45.3 32.3 5.6 5.3 10.2 6.1

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Fig. 4.

FESEM micrographs of the samples (a) A (b) B calcined at 900C.

(a)

(b)

Fig. 5. High-resolution transmission electron microscopy images of samples (a) A (b) B. The (a) corresponds to (111) plane of uorite phase while (b) shows the lattice fringes of (311) plane of pyrochlore La2Zr2O7.

(a)

(b)

Fig. 6.

Selected-area electron-diraction patterns of the samples (a) A (b) B.

ferent sizes, possibly indicating the presence of extra phases. We have not indexed the full pattern due to diculty in tting these spots into rings; only (111) plane was suitably indexed. The appearance of uniform rings in sample A is attributed to its ner crystallite sizes and homogeneous distribution.

IV.

Discussions

The lattice parameters calculated from XRD data for sample A and sample B from the rst four major reections were  and 5.3863 0.0008 A,  found out to be 5.2972 0.0051 A

respectively; noteworthy is the dierence (~1.7%) between them. The ionic radius of La3+ for coordination number 8 is  while that of Zr4+ showing sixfold coordination is 1.18 A  0.72 A.28 As a result, the replacement of La3+ ions by Zr4+ ions decreases the lattice parameter, hence shifting the peak positions toward higher angles. We have also noted an existing calculated pattern for the composition La0.1Zr0.9O1.9 (JCPDS le no. 01-082-1011). The presence of such a phase has been reported in experiments by Ion et al.29 It exists in cubic  and (Fm3m) structure with a lattice parameter of 5.1149 A,  Therefore, its (111) peak has the d spacing value of 2.9531 A. we believe sample A does not correspond to stoichiometric

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La2Zr2O7, but a slightly zirconium-rich phase which exists in the same uorite structure. There are two probable reasons for this: (a) some of the La-precursor (La3+ ions) is not participating in the reaction with Zr4+ as a result making the La/Zr ratio in the lanthanum zirconate less than unity (b) There is a depletion of both La3+ and Zr4+ ions with the former being depleted in a higher amount during the synthesis and/or during centrifugation process. The above argument on the basis of nonstoichiometry is further supported by the fact that La2Zr2O7 is not a line compound; rather it exists as an intermediate phase in the phase diagram to accommodate dierent ratios of La and Zr ions in the lattice.30 We have applied Vegards law31 to calculate the composition of the solid solution in A from its lattice parameter. Following Vegards law, researchers3234 have investigated and established a linear relationship between lattice parameter and composition in a wide range of solid solutions with isomorphous structures. In a similar way, Besikiotis et al.35calculated the x value of the uorite structured La1xZrxO2d which was detected as a secondary phase during the preparation of calcium-doped uorite and pyrochlore-structured lanthanum ceratezirconate solid solutions. To determine the composition of sample A, we have selected three compositions with isomorphous cubic structures from the calculated standard JCPDS data les, namely, ZrO2 (JCPDS le no. 49-1642), La0.5Zr0.5O1.75 (JCPDS le no. 01-075-0346), and La0.1Zr0.9O1.75 (JCPDS le no. 01-086-0337), belonging to the same space group (Fm3m). Assuming a linear variation in lattice parameter with composition across the solid solution region, the lattice parameters of the above-mentioned systems were t into a straight line. The results are shown in Fig. 7. The composition of the sample A is found to be La0.31Zr0.69O1.84 with a La/Zr ratio of 0.45. Now, we discuss the role of ultrasonication which nally led to all these structural and compositional changes in sample A compared to sample B for which an additional ultrasonication step was added. The coprecipitation process moves through a complex sequence of reactions nally leading to a loosely bound species of metal hydroxide compounds, possibly with an empirical formula of M1aM2b(OH)c(H2O)d, where M refers to the metal. It is also well-known that their reaction kinetics is strongly dependent on the process parameters (pH, temperature, stirring rate, etc.), which also nally dictate the rate of completion of such reactions. That is why it is common to observe some constituent precursor that retains their identity by not taking part in the reaction. This metal hydroxide complex may be visualized as a core of several nuclei which in turn grow on heating to higher temperatures and combine through solid-state diusion routes resulting in the desired multicationic oxide composition. The shock waves generated by ultrasonication success-

fully break these complex cores and facilitate their growth via diusion on heating. Therefore, sample B can be seen as a case where both nucleation and growth steps are competing with each other and nally the growth rate supersedes the nucleation. Eventually, this promotes fast kinetics and enhanced crystal growth. This will also indicate random growth and high agglomeration in sample B. Along with the XRD data, the SAED pattern in TEM conrms this trend. However, the same metal hydroxide complex core retains its identity in sample A and the growth of these nuclei is restricted. This is a case where rate of growth is hindered as many such nuclei are trapped in the core. As a result, this directs to a situation of more numbers of nuclei growing at a restricted rate compared to sample B nally leading to a smaller crystal size. The diused rings observed in the SAED pattern [Fig. 6(a)] also indicates that the size distribution is more homogeneous in sample A. The shock waves generated from ultrasonication are instrumental in breaking the complex core of the mixed hydroxide precipitates and thereby ensuring uniform mixing of all the precursors. Finally, this led to the correct stoichiometry of LZ powders. Thus, ultrasonication helps in fragmenting the precipitates into smaller fractions and nally each of them combines through solid-state diusion when heated up to 900C. This heating is necessary for phase development of the LZ powders but it also promotes random growth and agglomeration within the powders (compared to sample A). In case of sample A, made without ultrasonication, a major fraction of the nuclei retained their identity and their growth was restrained. However, the precursor mixing was not uniform and the nal LZ powder ended up with a composition depleted in Lanthanum. From XRD analyses, as discussed above, it is conrmed that the nal composition in sample A is depleted in Lanthanum. We have attempted to assign possible causes for this but are not certain why it is La which is preferentially depleted compared to Zr. We have also observed only monoclinic ZrO2 at low pH(<6) while conducting coprecipitation involving stoichiometric La and Zr precursors. It suggests that the kinetics of the conversion of hydroxide from Laprecursor is very slow and strongly pH dependent. This part of Lanthanum precursor could also be the one which is not taking part in reaction and retaining its identity as La (NO3)3. This fraction could get washed out from the system in sample A. But in sample B, due to eective mixing and breaking of lumps, they do not leave the system and show their presence by forming stoichiometric La2Zr2O7 along with the extra peaks of LaOCl. This LaOCl compound, as conrmed by XRD and HRTEM, is a product of exchange reactions between lanthanum nitrate and zirconium oxychloride. At times, we have also noticed the LaOCl peaks in sample A during our repeated trials. However, the peak shift was a constant phenomenon observed all the time for A. Therefore, the additional step of ultrasonication helps in eective washing and mixing which nally leads to enhanced crystal growth of stoichiometric La2Zr2O7 powders.

V.

Conclusions

Fig. 7. law.

Plot illustrating the composition of sample A using Vegards

Multigram scale synthesis of lanthanum zirconate powders was successfully carried out on a laboratory scale using coprecipitation route. Thermal analyses by DSC conrmed pH 11 to be the optimum for this coprecipitation process. An additional step of ultrasonication introduced during the washing stage facilitated the growth of stoichiometric La2Zr2O7. The sample prepared without ultrasonication showed signicant deviation from the parent stoichiometry and the reason was correlated with the faster depletion of La3+ ions from the system. Using Vegards law, the La/Zr mole ratio was approximated to 0.45 for this sample. Information obtained from XRD and HRTEM conrmed welldeveloped crystallinity in both the samples. Role of ultrasoni-

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cation was instrumental in achieving homogeneous mixing and composition for the lanthanum zirconate powders.

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