Measurement of thermal strain and total polarization estimation of lead zirconate titanatelead zinc niobate ceramics Muangjai Unruan,

Anurak Prasatkhetragarn, Yongyut Laosiritaworn, Supon Ananta, Athipong Ngamjarurojana, Rattikorn Yimnirun, Ruyan Guo, et al.
Journal of Materials Science Full Set - Includes `Journal of Materials Science Letters' ISSN 0022-2461 Volume 47 Number 15 J Mater Sci (2012) 47:5801-5805 DOI 10.1007/s10853-012-6479-y

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J Mater Sci (2012) 47:58015805 DOI 10.1007/s10853-012-6479-y

Measurement of thermal strain and total polarization estimation of lead zirconate titanatelead zinc niobate ceramics
Muangjai Unruan Anurak Prasatkhetragarn Yongyut Laosiritaworn Supon Ananta Athipong Ngamjarurojana Rattikorn Yimnirun Ruyan Guo Amar Bhalla

Received: 5 January 2012 / Accepted: 4 April 2012 / Published online: 24 April 2012 Springer Science+Business Media, LLC 2012

Abstract Thermal expansion properties have been measured for the ceramic lead zirconate titanatelead zinc niobate [(1 - x)PZT(x)PZN] in the temperature range of -100 to ?450 C. For all ceramics examined, the deviations from the straight line below Burns temperature were observed. The dynamic polarization uctuations in their relaxor compositions are believed to play a role in this deviation. Burns temperature was determined and the local polarization (Pd) was calculated from the thermal expansion data. Various aspects of understanding the polarization behavior and other effects in this ferroelectric system were examined and discussed.

Introduction There is a great deal of interest in relaxor ferroelectric materials due to the rich diversity of their electrical/ physical properties and possible applications in various technological devices [1]. Diffuse phase transition and a
M. Unruan (&) R. Yimnirun School of Physics, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand e-mail: muangjaiunruan@yahoo.com A. Prasatkhetragarn Department of Materials Science, School of Science, University of Phayao, Phayao 56000, Thailand Y. Laosiritaworn S. Ananta A. Ngamjarurojana Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand R. Guo A. Bhalla Department of Electrical and Computer Engineering, College of Engineering, The University of Texas at San Antonio, San Antonio, TX 78249, USA

strong frequency dependence of dielectric properties are the important characteristics of these materials, which are connected with their structural disorder and with the presence of polar nanodomains in non-polar matrix. There are three peculiar temperatures: Td, Tc, and Tm revealed in the structural investigations and physical property studies. Burns temperature or Td is the temperature below which randomly oriented polar nanoregions become detectable within the otherwise non-polar paraelectric phase of several proper ferroelectrics. This behavior was originally observed in BaTiO3 due to the characteristic anomaly of the refractive index [2]. The temperature where the ferroelectricparaelectric phase transition occurs is Curie temperature or Tc. The last important one is Tm, which is the temperature of the dielectric permittivity maximum, above which anisotropic relaxor state with random orientation of nanopolar domains occurs [2, 3]. The local polar regions (dynamic in nature) in the relaxor ferroelectric appear at a temperature Td, much higher than Tm, as suggested by Burns and Dacol [3]. These local polar regions, randomly oriented irreversible polarization (Pd) and a very small number of unit cells, grow with the reducing temperature. The local polarization exists above the transition temperature while disappears or becomes immeasurable above Burns temperature. A variety of experimental techniques, including refractive index measurements [2], Raman scattering [4], neutron powder diffraction [5], neutron elastic scattering [6], dynamic light scattering [7], and dielectric measurements [810] have been employed to conrm the existence and determine the value of Td. Thermal expansions which are related to the square of the polarization, xij Dl=l Qijkk P2 ; k 1

where xij is the thermal strain = Dl/l of a sample bar of length, l, Qijkk is the electrostrictive coefcient and Pk is the

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polarization, can be used to study phase transition, thermal expansion coefcient, and anisotropies to estimate the dynamic polarization in the relaxor systems [11, 12]. Therefore, Burns temperature and local (or dynamic) polarization can be accounted by this technique. Lead zirconate titanate (PZT) is the most popular ferroelectric material used in electronic devices [13]. Lead zinc niobate (PZN) is a relaxor ferroelectric material with frequency-dependent dielectric relaxation behavior, as well as diffuse phase transition at 140 C [14]. A single crystal of PZN shows extremely high dielectric and piezoelectric constants [15]. As both PZT and PZN possess excellent electrical properties, enhanced properties can thus be expected from ceramics in PZTPZN system. There have been many previous reports on the electrical properties of PZTPZN ceramics [1618]. In this study, we studied thermal expansion behavior of (1 - x)PZT(x)PZN (x = 0.1, 0.2, 0.3, 0.4, and 0.5) ceramics. Thermal expansion and thermal expansion coefcient data were then reported, which give strong evidence for a polarization existed far above Tc. Transition temperatures and Burns temperatures were estimated and the local polarizations were calculated from the thermal expansion data (Eq. 1).

Experimental The ceramics (1 - x)Pb(Zr1/2Ti1/2)O3(x)Pb(Zn1/3Nb2/3)O3 (with x = 0.10.5) used in this study were prepared from starting PZT and PZN powders by a conventional mixedoxide method via vibro-milling technique [19]. Perovskitephase PZN powders were obtained from the columbite method with zinc niobate (ZnNb2O6) selected as the precursor, while PZT powders were prepared by a simple mixed-oxide method [20]. For optimization purpose, the sintering was carried out at temperatures between 1200 and 1250 C for 2 h. Details of the processing and characterizations were provided elsewhere [1921]. All samples were cut in rectangular bars, typically 5 9 1 9 1 mm, to measure their thermal strain. The samples were placed inside a fused silica holder and heated at a rate of 2 C/min in temperature range of -100 to 450 C. A linear voltage-differential transformer (LVDT) dilatometer was used to measure the thermal strain as a function of temperature. The LVDT has an advantage over the other transformers as it gives a linear output for every unit displacement.

Results and discussion The thermal expansion (ST(T)) and thermal expansion coefcient aT(T) = dST(T)/dT as a function of temperature

for PZTPZN ceramics are shown in Fig. 1. The ferroelectricparaelectric phase transition temperature can also be determined from the thermal expansion coefcient. When the temperature approaches the ferroelectric paraelectric transition temperature, the thermal expansion coefcient anomaly of the materials can be noticed, as shown in Fig. 1. This is because near the ferroelectric transition the displacive nature of the transition of the dominant PZT inuences the crystalline lattice. Such responses in expansion upon heating over the ferroelectric transition range have been detected before by using X-ray diffraction and dilatometric measurement [22, 23]. In addition, the anomalies in thermal expansion are found at certain temperature, which are associated with the ferroelectricparaelectric phase transition temperature of this system. In relaxor rich compositions, x = 0.30.5, there is no clear anomaly of the thermal strain due to the nature of their diffuse phase transition. The widths of these anomalies depend on the composition of the materials. This behavior is generally not found in the normal ferroelectrics which generally show an abrupt discontinuity (rst orders) at the transition temperature and follow the linear relationship above the transition temperature [24]. It is found that, below transition temperature, the nature of thermal strain gradually changes with increasing PZN content. The thermal expansion is very low with low thermal expansion coefcient near room temperature as it is far below its transition temperature. Using the linear relationship behavior in high temperature range (dotted lines as seen above Td in Fig. 1), the Burns temperature can be clearly dened from the thermal strain plots. The small uctuations of the thermal expansion coefcients were found above the Burns temperature. The possible origin of this uctuation is not clear, but could be attributed to differential calculation error over small temperature range. Similar behavior has also been reported earlier [24, 25] in several cases. In addition, thermally generated defects could be considered as another possible origin of this uctuation [26]. Probably, the results of the thermal expansion coefcient calculation are thus not used for estimating accurately the Burns temperatures. Therefore, the thermal strain plots are thus found more suitable for Burns temperature identication. The values of Burns temperature (Td) were in the temperature range from 366 to 414 C depending on the PZT concentration and Burns temperature in general is much higher than the transition temperature. Due to the binary ferroelectric system, the values of Td could be quantitatively understood in relation to the end members. Therefore, the Td values of this system are approximately related more to Tc of PZT [11]. As shown in Table 1, the increasing of the difference between transition temperature maxima and Burns temperature was found with increasing the relaxor concentration (PZN

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Fig. 1 Thermal expansion (Dl/l) and thermal expansion coefcient (a) as a function of temperature for (1 - x)PZT(x)PZN ceramics, a x = 0.1, b x = 0.2, c x = 0.3, d x = 0.4, and e x = 0.5 (solid lines thermal expansion, long dash lines thermal expansion coefcient)

Table 1 Various electrical features and calculated coefcients from thermal expansion measurements in the (1 - x)PZT(x)PZN ceramics

Composition (x) 0.1 0.2 0.3 0.4

Td (C) 403 411 414 366 389

Tc (C) 347 327 330 252 223

TdTc (C) 56 84 84 114 166

Properties at room temperature a (910-6/C) 1.78 1.89 1.99 3.85 2.40 Pd (lC/cm2) 37 37 36 53 35 Ps (lC/cm2)a 15 15 26 23 23

From hysteresis measurement

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content), which is consistent with previous reports [24, 25]. As there is no polarization contribution above Burns temperature, the thermal strain gradually changes and becomes linear with temperature above Burns temperature. The rapid changes of thermal strain were found below Burns temperature close to the contributions from the dynamic polarization of the relaxor composition. The high temperature anomaly of thermal strain is caused by the symmetry change of the dominant PZT phase where as the differences reects the dynamic polarization arising of the relaxor component below the Burns temperature (Td). As shown in Fig. 1, for all compositions, the deviation from the straight line or linear relationship below the Burns temperature was observed. Similar behavior has been reported in other quadratic relationships with the polarization such as the deviation from the straight line at transition temperature in the refractive index and birefringence measurements [11]. By using Eq. (1), the randomly oriented irreversible polarization or local dynamic polarization (Pd) values can be obtained at various temperatures by analyzing the deviation of the strain from the high temperature linear behavior and by using Eq. (1) as mentioned "k above i.e., xij Dl=l Qijkk P2 : This equation can be described in the following relation "1 "2 "3 x11 Dl=l Q1111 P2 Q1122 P2 Q1133 P2 : 2

Fig. 2 Calculated total polarization (Pd) as a function of temperature for various (1 - x)PZT(x)PZN ceramics

PZN in the solid solution, the typical Tc of PZTPZN increases slightly and Td stays closer to it as the proper ferroelectric (PZT) dominates the properties. For the higher PZN content compositions, the properties follows the relaxor ferroelectric PZN. These results are consistent with the dielectric and ferroelectric properties of PZTPZN ceramics [1618].

As the measurements were performed on polycrystalline ceramics, therefore Q1111 = Q11, Q1122 = Q1133 = Q12 "1 "2 "3 " and P2 P2 P2 P2 . Hence, the nal form of Eq. (2) is as followed " x11 Dl=l Q11 2Q12 P2 : 3

Conclusions In this study, the thermal expansions of (1 - x)PZT (x)PZN were measured. The transition and Burns temperatures were determined from the thermal expansion coefcient and the thermal expansion, respectively. The results show that, at high temperature far above the transition, the thermal strain exhibited a linear relation with temperature. The deviation of the thermal strain was used to dene Burns temperature, ranging from 366 to 414 C depending on PZT/PZN concentrations. For all compositions, the Burns temperature was above the transition temperature. The temperature difference between Burns temperature and dielectric transition maxima temperature increased with increase in PZN component. The total polarization (including the dynamic component) can be calculated from the thermal expansion data. The results conrm that the local dynamic polarization exists in the relaxor compositions of PZTPZN ceramics.
Acknowledgements MU and RY acknowledge the nancial support from the Higher Education Research Promotion and National Research University Project of Thailand, Ofce of the Higher Education Commission and Suranaree University of Technology. This study was partially supported by the Industry/University Cooperative Research Center (IUCRC) in HDD Component, the Faculty of Engineering, Khon Kaen University and National Electronics and

The electrostrictive coefcients (Q) are determined in paraelectric phase and considered constant. Using the values of Q11 = 9.3512 9 10-2 and Q12 = - 3.1 9 10-2 m4/C2 [27] for a typical perovskite structure, Pd values were calculated and are shown in Fig. 2. It is found that the polarization calculated from the strain extends several degrees above Tc, indicating that some regions of the polarization are highly dynamic in nature. The local dynamic polarization (Pd) contribution to the thermal strain " as the nite square of polarization (P2 ) cannot be detected by a typical SawyerTower measurements [3]. The highest value of Pd was found in 0.6PZT0.4PZN composition; the morphotropic phase boundary (MPB) of this system. As shown in Table 1, Curie temperature (dominant PZT compositions) decreases and TdTc increases with increasing PZN (relaxor) content. This is because it has been known that the ferroelectricparaelectric phase transition of PZTPZN becomes more diffuse when the PZN content increases, which is an indication of a more pronounced relaxor behavior. For the low concentration of

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J Mater Sci (2012) 47:58015805 Computer Technology Center, National Science and Technology Development Agency (NSTDA). Additional support has also been provided through the NSF Grants DMR 0407462 and DMR 0844081, and INAMM Program. 5805 12. Bhalla AS, Guo R, Cross LE, Burns G, Dacol FH, Neurgaonkar RP (1990) Ferroelectrics 106(1):161 13. Moulson AJ, Herbert JM (2003) Electroceramics: materials, properties, applications. Wiley, Chichester 14. Bokov VA, Mylnikova IE (1961) Sov Phys Solid State 2:613 15. Uchino K (1998) Solid State Ion 108:43 16. Vittayakorn N, Rujijanagul G, Tunkasiri T, Tan X, Cann DP (2003) J Mater Res 18:2882 17. Fan H, Kim HE (2002) J Appl Phys 91:317 18. Vittayakorn N, Rujijanagul G, Tan X, He H, Marquardt MA, Cann DP (2006) J Electroceram 16:141 19. Ngamjarurojana A, Khamman O, Yimnirun R, Ananta S (2006) Mater Lett 60:2867 20. Yimnirun R, Tipakontitikul R, Ananta S (2006) Int J Mod Phys 20:2415 21. Ngamjarurojana A, Khamman O, Ananta S, Yimnirun R (2008) J Electroceram 21:786 22. Imai K (1997) J Phys Soc Jpn 43:1320 23. He Y (2004) Thermochim Acta 419:135 24. Wongmaneerung R, Guo R, Bhalla A, Yimnirun R, Ananta S (2008) J Alloys Compd 461:565 25. Wongsaenmai S, Yimnirun R, Ananta S, Guo R, Bhalla A (2008) Mater Lett 62:352 26. Mueller V, Jager L, Beige H, Abicht HP, Muller T (2004) Solid State Commun 129:757 27. Abe T, Reed ML (1994) In: Proceedings of the IEEE international conference on MEMS, p 164

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