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3 Copyright Transfer Statement The copyright to this article is transferred to Springer (respective to owner if other than Springer and for U.S. government employees: to the extent transferable) effective if and when the article is accepted for publication. The author warrants that his/her contribution is original and that he/she has full power to make this grant. The author signs for and accepts responsibility for releasing this material on behalf of any and all co-authors. The copyright transfer covers the exclusive right to reproduce and distribute the article, including reprints, translations, photographic reproductions, microform, electronic form (offline, online) or any other reproductions of similar nature. An author may self-archive an author-created version of his/her article on his/her own website and his/her institution s repository, including his/her final version; however he/ she may not use the publisher s PDF version which is posted on Furthermore, the author may only post his/her version provided acknowledgement is given to the original source of publication and a link is inserted to the published article on Springer s website. The link must be accompanied by the following text: The original publication is available at Please use the appropriate DOI for the article (go to the Linking Options in the article, then to OpenURL and use the link with the DOI). Articles disseminated via are indexed, abstracted, and referenced by many abstracting and information services, bibliographic networks, subscription agencies, library networks, and consortia. After submission of this agreement signed by the corresponding author, changes of authorship or in the order of the authors listed will not be accepted by Springer d&p 02/05 Journal Journal of Electroceramics Title of article Dielectric and piezoelectric properties of lithium sodium niobate Na Author(s) Li Yin Zheng Guo Cao Author s signature Date

4 Testsite AUTHOR'S PROOF file://d:\programs\metadata\temp\eec79163.htm Page 1 of 2 4/25/2007 Metadata of the article that will be visualized in OnlineFirst 1 Article Title Dielectric and piezoelectric properties of lithium sodium niobate Na 1 x Li x NbO 3 lead free ferroelectric ceramics 2 Journal Name Journal of Electroceramics 3 Family Name 4 Particle 5 Given Name G. R. 6 Suffix 7 Organization Chinese Academy of Science Li 8 Corresponding Division The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Author Institute of Ceramics 9 Address Shanghai , People s Republic of China 10 Organization The Pennsylvania State University 11 Division Materials Research Institute 12 Address University Park 16802, PA, USA 13 grli@sunm.shcnc.ac.cn 14 Family Name 15 Particle 18 Author Organization Chinese Academy of Science Yin 16 Given Name Q. R. 17 Suffix 19 Division The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics 20 Address Shanghai , People s Republic of China Family Name 23 Particle Zheng 24 Given Name L. Y. 25 Suffix 26 Author Organization Chinese Academy of Science 27 Division The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics 28 Address Shanghai , People s Republic of China Family Name Guo 31 Particle 32 Given Name Y. Y. 33 Suffix

5 Testsite AUTHOR'S PROOF file://d:\programs\metadata\temp\eec79163.htm Page 2 of 2 4/25/ Organization Chinese Academy of Science 35 Division The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Author Institute of Ceramics 36 Address Shanghai , People s Republic of China Family Name 39 Particle Cao 40 Given Name W. W. 41 Suffix Author 42 Organization The Pennsylvania State University 43 Division Materials Research Institute 44 Address University Park 16802, PA, USA Received 47 Schedule Revised 48 Accepted 49 Abstract High density sodium lithium niobate lead free ceramics near the morphtropic phase boundary [Na x Li 1 x NbO 3, (LNN), x = 0.12] were prepared by the solid 50 Keywords separated by ' - ' 51 Foot note information state reaction method. XRD patterns showed that the lattice structures were changed after polarization. The temperature dependence of the dielectric constant and dielectric loss, pyroelectric coefficient and DSC curves of LNN ceramics showed that there exist three phase transitions from room temperature up to the Curie temperature. The hysteresis loop and piezoelectric properties have also been measured and discussed. Na x Li 1 x NbO 3 - Piezoelectric - Dielectric - Ferroelectric - Phase transition

6 AUTHOR'S PROOF 1 2 J Electroceram DOI /s x JrnlID 10832_ArtID 9163_Proof# 1-25/04/ Dielectric and piezoelectric properties of lithium sodium 5 niobate Na 1 x Li x NbO 3 lead free ferroelectric ceramics 6 G. R. Li & Q. R. Yin & L. Y. Zheng 7 Y. Y. Guo & W. W. Cao 9 # Springer Science + Business Media, LLC Abstract High density sodium lithium niobate lead free ce- 13 ramics near the morphtropic phase boundary [Na x Li 1 x NbO 3, 14 (LNN), x=0.12] were prepared by the solid state reaction 15 method. XRD patterns showed that the lattice structures 16 were changed after polarization. The temperature depen- 17 dence of the dielectric constant and dielectric loss, 18 pyroelectric coefficient and DSC curves of LNN ceramics 19 showed that there exist three phase transitions from room 20 temperature up to the Curie temperature. The hysteresis 21 loop and piezoelectric properties have also been measured 22 and discussed. 23 Keywords Na x Li 1 x NbO 3. Piezoelectric. Dielectric. 24 Ferroelectric. Phase transition 25 1 Introduction 26 Sodium Niobate, NaNbO 3 is in orthorhombic phase at room 27 temperature its antiferroelectric-to-paraelectric phase tran- 28 sition (tetragonal) takes place at about 354 C (Curie 29 temperature). Lithium Niobate LiNbO 3 has a trigonal 30 symmetry at room temperature and shows a second-order 31 phase transition at about 1,200 C. The solid solution 32 Na x Li 1 x NbO 3 (LNN) ceramics is a very interesting G. R. Li (*) : Q. R. Yin : L. Y. Zheng : Y. Y. Guo The State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai , People s Republic of China grli@sunm.shcnc.ac.cn G. R. Li : W. W. Cao Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA material due to its lead free composition and high acoustic velocity, which is useful in high frequency applications. However, phase structures of LNN are very complex, they are strongly dependent on the Li +1 substitution ratio. It is know that the orthorhombic phase and trigonal phase coexist in the morphtropic phase boundary (MPB) composition of LNN (x=0.12). Many papers have reported the limitation of Li 1+ in LNN solid solutions [1, 2], and the related phase diagram [3, 4], but only a few papers dealt with dielectric, piezoelectric, and ferroelectric properties, and the relations of these properties to the phase transitions [5]. Recently, there is an increasing demand for lead-free piezoelectric ceramics, hence, it is important to gain a better understanding on the dielectric and piezoelectric properties of LNN ceramics and the structure-property relation [6, 7]. In this paper, we report the fabrication of dense LNN ceramics by the solid reaction process, and give the dielectric, piezoelectric, ferroelectric properties. Related phase transitions will also be discussed. UNCORRECTED PROOF 2 Experimental LNN (compositions with x=0.06, 0.10, 0.12, 0.15, and 0.20, are abbreviated as LNN6,, LNN12, LNN15, and LNN20, respectively) ceramics were prepared by the conventional mixed oxide method. High purity powders were weighted according to the stoichiometric ratio of the composition and mixed in a ball mill, calcined at 850 1,000 C. The ceramic specimens were finally sintered at 1,160 1,360 C. Ag electrodes were printed on the sintered samples and fired at 750 C. These samples were poled at the electric field of 6 kv/mm in a silicone oil bath at 120 C for half an hour

7 AUTHOR'S PROOF JrnlID 10832_ArtID 9163_Proof# 1-25/04/2007 J Electroceram 64 The shrinkage of ceramics was measured by the high 65 temperature shrinkage instrument. Structural phases were 66 characterized by X-ray diffraction using a Guinier-H agg 67 camera with Cu Kα1 radiation. Hysteresis loops were 68 measured by the Sawyer-Toywer circuit. The temperature 69 dependence of the dielectric constant and loss tan δ was 70 measured at a frequency of 1 khz with a measuring field of 71 about 1 V/mm using an automated dielectric measurement 72 system with an LCR meter (Tonghui Electric TH2817). 73 Piezoelectric constant d 33 was measured by a quasi-static 74 d 33 meter (Institute of Acoustics, Academia Sinica, ZJ-2) Results and discussion 76 The sintering temperatures of LNN ceramics were found to 77 be strongly dependent on the Li +1 ratio. Figure 1 is the 78 shrinkage of LNN ceramics (x=0.10, 0.12, and 0.15). These 79 sintering behaviors is due to the smaller radii of Li (0.82 A) compared to that of Na 1+ (1.10 A), which causes 81 lattice distortion and/or produces defects in the structure of 82 LNN, resulting in the decreasing of diffuse active energy. 83 The liquid phase occurred at lower temperatures as the ratio 84 of LiNbO 3 increases, which makes the grain grow easer. 85 Dense LNN ceramics have been obtained. 86 XRD patterns were used to investigate the crystal 87 structure of non-poled and poled LNN ceramics. Results 88 showed that relative peak intensities and lattice structures 89 were quite different before and after poling. Figure 2 is the 90 XRD patterns of the non-pole and the poled 91 ceramics. Intensities of (020) and (112) peaks is quite 92 different, in addition, (220) and (004) peaks of the non- 93 poled merged into one peak after poling. These 94 differences indicated that domains were switched during 95 poling, resulting in the change of peak intensities. The 96 merging of (220) and (004) peaks may imply that a 97 structural phase transition occurred under high electric 98 fields. 4 Figure 3 shows the temperature dependence of the dielectric constant and loss for non-poled LNN ceramics near the MBP (i.e.,, LNN12, and LNN15). One can see that one phase transition peak appeared for each case in the temperature range from 280 to 400 C. Specifically, the peak temperatures were 359, 374 and 376 C for, LNN12, and LNN15, respectively. There were no peaks in the temperature range from room temperature to 280 C. However, a shoulder could be found at a temperature lower than the Curie temperature, the locations of the shoulder were in the temperature ranges of C, C, and C for, LNN12, and LNN15, respectively. The dielectric loss peak temperature was 324, 344 and 328 C for, LNN12 and LNN15, respectively, close to the corresponding beginning point of the shoulder. Figure 4 is the temperature dependence of the dielectric constant and loss for poled LNN ceramics. Although their Curie temperatures were nearly unchanged compared to the non-poled cases, the shape of the shoulders changed greatly. The shoulder in the dielectric peak of LNN15 even became a peak and its intensity exceeds the peak at the Curie temperature. The temperature dependence of dielectric loss for all LNN ceramics showed two peaks, corresponding to the shoulder temperature and the Curie temperature. In addition, both dielectric constant and loss UNCORRECTED PROOF (110) poled no-poled (020) (112) (220) θ ( ο ) Fig. 2 The XRD pattern of ceramics (004) (220) (130) (310) (114) (132) (024) Print will be in black and white Print will be in black and white Shrinkage (%) LNN12 LNN Temperature ( O C) Fig. 1 Shrinkage of the LNN ceramics (a) Dielectric Constant ( 10 3 ) un-poled LNN12 LNN (b) Dielectric Loss LNN12 LNN15 Un-Poled Temperature ( o C ) Temperature ( o C ) Fig. 3 Temperature dependence of dielectric constant (a) and dielectric loss (b) for non-poled LNN ceramics

8 AUTHOR'S PROOF J Electroceram JrnlID 10832_ArtID 9163_Proof# 1-25/04/2007 (a) Dielectric Constant ( 10 3 ) Temperature ( o C) Temperature ( o C) Fig. 4 Temperature dependence of dielectric constant (a) and dielectric loss (b) for poled LNN ceramics 124 showed a peak in the temperature range from room 125 temperature to 280 C for poled LNN ceramics. Thus, 126 three peaks were observed in poled LNN ceramics, while 127 there were only two for non-poled LNN ceramics. 128 Figure 5 shows the DSC curves for poled LNN ceramics, 129 the DSC curve for the non-poled LNN12 was also plotted 130 in the figure for comparison. It was clear that all of LNN 131 ceramics showed two peaks, indicating that there exist two 132 first order phase transitions. The Curie temperature 133 corresponding to the second peak, was the same for non- 134 poled and poled LNN12. Comparing the poled and non- 135 poled LNN12, the area under the curve, reflecting the phase 136 transition energy, in the first peak was little larger than that 137 in the second peak. These results were consistent with the 138 temperature dependence of dielectric properties of LNN 139 ceramics. However, a phase transition in the temperature 140 range from room temperature to 280 C was not observed 141 by the DSC measurement. 142 Figure 6 is the temperature dependence of the pyro- 143 electric coefficient of LNN12. It shows a peak at about C, close to its dielectric loss peak temperature. To 145 confirm the characteristic of this peak, piezoelectric 146 property was checked using a poled ceramics 147 with d 33 =42 pc/n. The sample was annealed at 165 C DSC ( a.u.) poled LNN12 LNN15 poled LNN Poled LNN12 (b) Dielectric Loss Poled LNN12 LNN15 for several hours and the d 33 value was not changed. Thus, this peak corresponds to a ferroelectric-to-ferroelectric phase transition. These phase transitions were observed by Nitta before [1], who used temperature dependence of XRD pattern to identify that the phase transition in the temperature range from room temperature up to the Curie temperature corresponds to a structural transition from rhombohedra-toorthorhombic phase. Our results showed that this is a ferroelectric-to-ferroelectric phase transition. The other two peaks in the temperature dependence of DSC and dielectric properties correspond to orthorhombic to tetragonal phase, and tetragonal to Cubic phase transitions. Figure 7 shows the hysteresis loops of. The shape of the hysteresis is typical for a ferroelectric material. An interesting point is the sudden change of the loop size passing a critical field level. The loops have almost the same coercive field for different applied voltages from 2,500 V up to 3,500 V, their residual polarization only changed slightly. However, when the voltage level is increased to 4,000 V, the size of hystersis loop suddenly increased. Remanent polarization almost doubled (0.62 mc/m 2 )andthecoercivefield UNCORRECTED PROOF 332 poled un-poled LNN Fig. 5 DSC curves of LNN ceramics Temperature ( o C) p (10-8 C/cmK) Polarization (C/m 2 ) V 3000V 3500V 4000V Temperature ( o C) Fig. 6 Temperature dependence of pyroelectric coefficient x x x x10 6 E ( V/m ) Fig. 7 Hysteresis loop of ceramics under different switching electric fields

9 AUTHOR'S PROOF JrnlID 10832_ArtID 9163_Proof# 1-25/04/ increased about 50% (2,700 V/mm). The rapid change of 171 hystersis loop implies that the lattice structure undergone a 172 phase transition under high electric fields. In case of, 173 the structural phase transition occurs under an electric fields 174 higher than 2,700 V/mm. J Electroceram ferroelectric phases but the exact lattice structure change still needs to be identified. Acknowledgements The authors gratefully acknowledge the finance support of the National Basic Research Program of China (2002CB613307) Summary 176 High density LNN piezoelectric ceramics have been 177 prepared and characterized. Results of dielectric, piezoelec- 178 tric, pyroelectric, and DSC measurements showed that there 179 exist three phase transitions. A structural phase transition 180 was induced by high electric fields in the poled sample, 181 which resulted in different XRD patterns, and different 182 temperature dependence of the dielectric constant and loss 183 for poled and non-poled LNN ceramics. From our 184 preliminary analysis, this phase transition is between two References 1. T. Nitta, T. Miyazawa, J. Am. Ceram. Soc. 55, 636 (1971) 2. R.R. Zenfang, J. Appl. Phys. 48, 3014 (1977) 3. R.V. Muehll, Solid State Commun. 31, 151 (1979) 4. L. Pardo, P. Duran-Martin, J.P. Mercurio, L. Nibou, B. Jimfinez, J. Phys. Chem. Solids. 58, (1997) 5. M.A.L. Nobre, S. Lanfredi, J. Phys. Chem. Solids 62, 1999 (2001) 6. T. Wada, K. Tsuji, T. Saito, Y. Matsuo, Jpn. J. Appl. Phys. 42, 6110 (2003) 7. T. Takeda, Y. Takahashi, N. Wada, Y. Sakabe, Jpn. J.Appl. Phys. 42, 6023 (2003) UNCORRECTED PROOF

10 AUTHOR QUERY AUTHOR PLEASE ANSWER QUERY. No Query. UNCORRECTED PROOF