DEVELOPMENT OF HIGH ELECTRICALLY INDUCED STRAIN AND LOW HYSTERIC LOSS COMPOSITIONS FOR ACTUATORS

Surya M.Gupta, Z. Xu and Dwight Viehland

Department of Materials Science and Engineering, and Materials Research Laboratory, L University of Illinois at Urbana Champaign, I 6 1801
ABSTRACT - Elecmcally-induced strain and polarization studies of La modified (1 to 10 at%) morphotropic phase boundary Pb(Mgll3N~2/3)03-PbTi03(PMN-PT) ceramics have been performed. Charge imbalance due to La3+ substitution on the A-site was compensated by : (a) B-site vacancies, and (b) changing Mg/Nb/Ti ratio on the B-site. Tendencies of non stoichiometric ordering were found to increase when La was compensated by B-site vacancies (LaPMN-PT) and to decrease for La compensation by changing MgMblTi ratio (PLMN-PT). Quantitative analysis using Energy Dispersive X-ray Spectroscopy (EDS) revealed a continuous decrease in Nb and corresponding increase in Ti contents for La-PMN-PT with increasing La substitution. For PLMN-PT, no change in the B-site cation concentration was noticed. The spontaneous polarization and remanent strain were found to be higher for La-PMN-PT than PLMN-PT at low La contents (< 8at?!) and to be lower at high La contents (> 8at%). In this study, the composition 2/65/35 was found to for Laexhibit a maximum remanent strain of 1.6 x for PLMN-PT. The effect of non PMN-PT and 1.4 x stoichiometric ordering on the dielectric propexties and phase stability were then investigated for the directed purpose of developing new high-performance high-strain actuators with good micropositioning capabilities.

and 35 at%, and normal micron-sized ferroelectric domains for PT contents greater than 35 at%. In addition, La-modification of PMN-PT was found to result in the evolution of polar nanodomains and relaxor characteristics from the tweed-like structures. Other studies by Hilton et al. [8] reported a reduction in the 1/2[111] reflection intensity of PMN upon addition of PT. It was then concluded that Ti modification reduces the driving force for the ordering process. The purpose of the present study was to develop PMN based materials with higher electrically induced strains and lower hysteretic losses for actuators applications. Several different charge compensation mechanisms for La3+ substitution onto the A-site were studied: (i) by B-site vacancies while maintaining the Mg/Nb/Ti ratio unchanged, and (ii) by changing the Mg/Nb/Ti ratio while maintaining the B-site vacancy concentration fmed. The effect of these different Lacompensation mechanisms on the electrically induced straia and polarization were then determined. Experimental The specimens studied in this investigation were fabricated according to the formula: (a) Pbl-x Lax [(Mg1/3M2/3)0.65 Ti 0.3511-x/4 0 3 (La-Pm-PT x/65/35) for OcxcO.1 where La3+ is compensated by creating B-site vacancies, and (b) Pbl-xLax [(Mgl +x/3M2-&0.65Ti( 1-d4)0.35103 ( P L m - P T d65/35) for OcxcO.1 where La3+ is compensated by changing Mg/b/Ti ratio on the B-site. The purity of the starting materials was 99.9%, except for La203 whch was 99.99%. The specimens were prepared by the columbite precursor method [9]. The columbite precursor (MgNb206) was first prepared by mixing predetermined amounts of MgO and N b 2 0 5 in isopropanol and ball milling for 5 hours using a ZrO2 p d i n g media. The slurry was b e d at 80 OC and the powder then calcined at 1100 O C for 4 hours. Single phase formation of MgNb206 was confirmed by x-ray difiaction (XRD). The columbite precursor was then mixed and ball milled with predetermined amounts of PbO, Ti02 and La203 powders and calcined at 850 OC for 4 hours. The calcined powders were mixed again and pressed into cylinders using polyvinyl alcohol (PVA) as a binder under a hydrostatic pressure of 25 kpsi. These cylinders were fired at 1250 OC for 4 hours after binder burnout at 450 OC for 3 hours. Firing was performed in a closed alumina crucible, in order to

Introduction A wide varieties of actuators applications in advanced precision engineering have stimulated need for a material with high strain and minimum hysteresis loss [l-21. Piezoelectric actuators are capable of producing high displacement in comparison to that in electrostrictive actuators [3]. The main drawback of piezoelectric actuators is their significantly high hysteresis loss. Therefore, intensive studies have been directed in developing electrostrictive materials. The newly developed materials are lead magnesium niobate (PMN) based ceramics [4-51. This material does not contain domains, and so does not show hysteresis loss when a field is reversed. Lead magnesium niobate, a high permittivity ferroelectric material, shows large electrostrictive effect near the temperature of its dielectric maximum. The transition temperature can be shifted near to room temperature by aIlexing with lead titanate (PbTi03). 0.9 PMN-0.1 PbTi03 has been reported [6] to exhibit strains up to 0.1% without hysteresis at room temperature under an electric field of 15 KV/cm. Structural studies of PMN as a h c t i o n of lead titanate (PT) content have previously been reported by Viehland et al. [7]. Viehland et al. demonstrated the presence of polar nanodomains for PT contents less than 30 at%, tweed like structure for PT contents between 30

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minimize lead oxide loss. The calcined and sintered specimens were analyzed by XRD (Rigaku, D-max CuKa radiation) for second phase formation. The sintered blocks were then cut into t i disks and hn polished on different grades of emery papers to obtain parallel surfaces. The polished surfaces were ultrasonically cleaned to remove dust particles. Electroding was carried out by sputtering gold, followed hn by a t i coating of air dried silver paint. Field induced longitudinal strain measurements were made using a linear variable differential transformer (LVDT)at 10 Hz frequency. Electricallyinduced polarization studies were performed using a modified Sawyer-Tower technique. Scanning electron micrographs were taken from fractured and chemically etched surfaces. Section of sintered specimens were etched by HC1 (Conc.) for two minutes. The chemically etched and fractured surfaces were sputtered with gold and palladium. The chemically etched surfaces were used for quantitative standardless energy dispersive spectroscopy and the fractured surfaces were used for grain size and morphology determinations. Both studies were done using a Zeiss DSM-960 scanning electron microscopy (SEW. TEM specimens were prepared by ultrasonically drilling 3-mm discs which were mechanically polished to -100 p. The center portions of these discs were then further ground by a dimpler to 10 pm, and argon ion-milled to perforation. Specimens were coated with carbon before examination. The TEM studies were done on a Phillips EM-400 microscope operating at an accelerating voltage of 120 kV.

10165135 and L-5/65/35, 1/2{111) superlattice reflections are clearly apparent. However, only weak diffuse reflections were observed for 5/65/35 and L10/65/35. In general, it was observed that the superlattice reflection intensity increased with increasing La-content between 0 and 10 at.% for compositions in the La-PMN-PT sequence, however the intensity decreased for compositions in the PLMN-PT sequence. SEM images of fracture surfaces for 0165135, 5/65/35, 10165135,L-5/65/35, and L-10/65/35 are shown in Figures 2(a)-(e), respectively. It should be noticed that the micrographs for 5/65/35 and 10165135 (Figures 2(b) and (c)) clearly demonstrate a secondary phase, as indicated by arrows. However, no secondary phase was observed for L-5/65/35 and L-10/65/35 (Figures 2(d) and (e)). The secondary phase can be identified as pyrochlore on the basis of its octahedral morphology [lo]. The composition of the pyrochlore phase was quantitativelydetermined by EDS on chemically etched sections of sintered ceramics. The composition of the pyrochlore phase was determined to be

Relative to the composition of the perovskite grains, the pyrochlore composition is deficient in Mg and Ti, but rich in Nb. Typical compositions of the perovskite grains for 10/65/35 and L-10/65/35 were determined to be Pb0.98LaO.lNb0.41MgO.15Ti0.3502.98 and Pb0.96La0.1Nb0.46Mg0.12Ti0.3403.08, respectively. The compositions of the perovskite grains for 0165135, 5/65/35 and L-5/65/35 are tabulated in Table I. It would seem apparent for La-PMN-PT that La3+ is compensated on the B-site positions by the outward diffusion of Nb5+ and the inward diffusion of Ti+4. Consequently, for the La-PMN-PT sequence, Lasubstitutionresults in Nb-rich and Nb-poor regions. The Nb-rich regions are pyrochlore, consistent with earlier investigation [lo], whereas the Ti-rich remain perovskite. For lower La-content PLMN-PT compositions, no evidence for the diffusion of B-site cations was observed. However, evidence for an outward diffusion of Mg and a small inward diffusion of Nb were observed at higher La-substitutions (>8 at%) by changes in composition. Small degrees of inward diffusion of Nb should favor pyrochlore phase, although this was not found to be the case for L-10/65/35. XRD was used to determine the amounts of pyrochlore phase present in each specimen and are presented in Table 1. The ratio of relative intensities of the (222) pyrochlore peak (Ipyro) and the (110) perovskite PMN peak ( I p m ) were used to determine

Results and Discussion Figures l(a)-(e) illustrate room-temperature bright field images for La-modified PMN-PT compositions of 0/65/35, 5/65/35, 10/65/35, L-5/65/35 and L-10165135, respectively. [Specimens in which La3+ was compensated by B-site vacancies and changing Mg/Nb/Ti ratio are represented by x/65/35 and L-x/65/35, respectively.] For the composition 0165135 (Figure l(a)), ferroelectric domains were observed. These domain structures confirm the existence of longrange ferroelectricorder. On La-substitution, long-range ferroelectric order was broken down and polar nanodomains became the stable domain-like structure, as can be seen in Figures l(b)-(e). The average size of these polar nanodomains decreased with increasing Lacontent for compositions in both La-PMN-PT and PLMN-PT sequences. For L-5/65/35 (Figure 1(d)), ferroelectric domains (indicated by an arrow) were found to coexist with polar nanodomains, however no such coexistence was observed for 5/65/35. <1 IO> SAED patterns are shown in Figures l(a)-(e) for 0165135, 5/65/35, 10/65/35, L-5/65/35, and L-10/65/35, respectively. In these figures, the presence of superlattice reflections are indicated by arrows. For

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the volume fraction of pyrochlore present. From Table

1, it should be noticed that the volume fraction of

pyrochlore phase was increased from 0% to 14% for LaPMN-PT as La-content was increased from 0 to 10 at%. However, for PLMN-PT, no pyrochlore peaks were detected as the La-content was increased from 0 to 8 aPh, but a small amount of pyrochlore phase (-1 at.%) was detected for L-10/65/35. These result are consistent with the compositional findings presented in section III.1,where the development of a secondary pyrochlore phase in La-Ph4N-PT was attributed to the formation of Nb-rich and Nb-poor regions.
TABLE 1 Comparison ofperovskiugrain compositionsand pyrochkm phase cooce~uation with variaticm of La-subsitutionf a La-PMN-PT and PLMN-PT

compensation by B-site vacancies resulted in better electromechanicalperformance characteristics, suitable for high-power transducers. Acknowledgements This work was supported by the Office of Naval Research ( O m ) under contract No. N00014-951-0805 and by Naval Undersea Warfare Center contract No. N66604-95-C-1536. The use of the facilities in the Center for Microanalysis in Materials Research Laboratory at the University of Illinois at UrbanaChampaign is gratefully acknowledged.
1. K. Uchino, Y.Tsuchiya, S. Nomura, T. Sato, H. Ishikawa and 0.

References

0/65/35 5/65/35 1016565 L-5/65/35 L- 10/65/35

OmpoSltlOns pbl .07MRl. 18Nbo.44Tb.3102.97 pbl .OOh.@gO. 18%.4$%.3202.99

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Pbo.96h.mg0.26%.42T%.3 102.96 Pbo.96h.l@gO.l2%.46Ti0.3403.08

The value of ~ m a x KV/cm) is plotted (30 against La-content for La-PMN-PT and PLMN-PT in Figure 3. In this study, the composition 0/65/35 was found to exhibit a maximum electrically-inducedstrain of 3x10-3. In this figure, it can be noticed that Lasubstitution decreases ~ ~ ( kV/cm) more rapidly for 3 0 PLMN-PT than La-PMN-PT. The values of the maximum strain under a drive of 3OKVlcm can be seen to be increased by minor additions of La (upto 2 at%), in addition the degree of hysteresis was found to remain nearly constant for La-PMN-PT. Upon increasing the La content to 5 at%, a significant reduction in the degree of hysteresis was observed. On further increment of the La content, the value of emax was dramatically reduced. Clearly, in terms of electromechanical performance, specimens prepared by B-site vacancy compensation are superior. These specimens have higher induced strains and lower dielectric constants.

Ikeda. "Deformable Mirror Using the PMN Elecwstrictor". Auul. Oatics 20.3077 (1981). 2. A. K & , "A Piezoelectric Ulnasonic Motor", Jpn. J. Appl. PhyS.. 24, Suppl. 24-2,739 (1985). 3. K Uchino, UPiezoelectric and Electrostrictive Actuators", Proc. IEEE ,610 (1981). 4. S. Nomura and K. Uchino, "Electrostrictive Effect in Pb(Mglfim/3)03-Type Materials," Ferroelectrics, 41, 117 (1982). 5. S Nomura and K. Uchino, "Recent Application of PMN-Based . Electrostrictors", Ferroelectrics, 50,523 (1983). 6. L. E. Cross, S.J. Jang, R. E. Newnham, S. Nomura and K. Uchino, "Large Electrostrictive Effects in Relaxor Ferroelectrics", Ferroelectrics, 23, 187 (1980). 7. D. Viehland, M.-C. Kim, Z. Xu, and J.-F. Li, "Long-time metastable tweedlike precursors and paraelectric clusters in ferroelectrics containing strong quenched randomness", Appl. Phys. Lett. 67,247 1 (1995). 8 A. D.Hilton, D. J. Barber, C. A. Randall and T. R. Shrout, "On . short range ordering in the perovskite Lead Magnesium Niobate", J. Mat. Sci., 25,346166 (1990). 9. S. L. Swam and T. R. Shrout, "Fabrication of perovskite Lead Magnesium Niobate", Mat. Res. Bull., 17, 1245-50 (1982). 10. J. Chen and M. P. Harmer, "Microstructure and dielectric properties of Lead Magnesium Niobate diphasic mixtures", J. Am. C m Soc.. 73,68-73 (1990).
r r

-La-PMN-PT 3s X

Conclusions Non-stoichiometric ordering in PMN-PT compositions close to the MPB his been investigated by TEM, as a h c t i o n of La-content using various compensation mechanisms. Compensation by B-site vacancies was found to result in secondary pyrochlore phase formation, enhanced B-site cation ordering, and a decrease in Nb-content and an increase in Ti-content of the perovskite phase. Electrically induced strain and polarization measurements demonstrated that nonstoichiometric ordering leads to reduction in and the spontaneous polarization. A small amount of Lasubstitution (< 2 at%) on the A-sites in PMN-PT (65/35) was proven to enhance the remanent polarization, whereas large La-contents (> 5at%) lead to the development of Nb-rich and Nb-poor regions and reduces Em= for La-PMN-PT. It was also shown that

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Figure 3 Comparison of electrically induced strain (at 30 KV/cm) for various La-PMN-PT and PLMN-PT, x/65/35 compositions with La-contents between 0 and 10 at%.

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