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Manuscript number MRB_2017_1497

Title Influence of densification process on structural, microstructural and dielectric


properties of PLMN-PT:0.5Er ceramics

Article type Research Paper

Abstract
Ferroelectric ceramic of 0.5% Er3+ doped and un-doped (1-x)[Pb(1-y)Lay(Mg1/3Nb2/3)O3]-xPbTiO3 (PLMN-PT) were
prepared by solid state reaction using the columbite method and densified by conventional sintering (CS), uniaxial hot
pressing (HP) and spark plasma sintering (SPS). In this work, we reviewed and discussed the influences of
densification process on microstructural, structural and dielectric properties of the ceramics. It was observed that fully
compacted specimens were obtained without porosity and homogeneous microstructure. Density of ceramics close to
theoretical value (more than 99%) could be reached easily by HP. Heat treatment process in ceramics obtained by
SPS eliminates the dark colour and improves transparency. Also, its reviewed and discussed the influences of
densification process on microstructural, structural properties of the ceramics, finding the electrical properties are
favoured by HP.

Keywords PLMN-PT, Microstructural, Structural, Dielectric, Densified.

Manuscript category Electroceramics, structure analysis, other

Corresponding Author Juan David Rincon

Corresponding Author's Univ Antioquia


Institution

Order of Authors Juan David Rincon, Fernando Londono, Ducinei Garcia, Jose Eiras, Diego
Viana

Suggested reviewers Miryam R Joya, Jos de los Santos Guerra, Jesus Eduardo Vega Castillo

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27/04/2017

Dear Materials-research-bulletin

Please find enclosed the MS Influence of densification process on structural,

microstructural and dielectric properties of PLMN-PT:0.5Er ceramics3 which we

would like to be reviewed for publication in the Materials-research-bulletin. I am a

professor of the Universidad de Antioquia, I am a physics and I work with ferroelectric

ceramics, powder synthesis and structural, microstructural, dielectrical and electro-

optical characterization on ceramics

Thank you very much for your attention and please do not hesitate in contact us if you
need any more interest.

Best regards

Dr. Juan David Rincon

Name: Juan David Rincon

Address: Calle 67 No. 53-108 Of. 5-339

City: Medelln

State: Antioquia-Colombia

Phone: 0057-3127209069

Email: david.rincon@udea.edu.co
GRAPHICAL ABSTRACT
Available online at www.sciencedirect.com

Influence of densification process on structural, microstructural and


dielectric properties of PLMN-PT:0.5Er ceramics
J.D.Rincona, F. A. Londooa, D.S.F.Vianab, J. A. Eirasb and D. Garciab
a Grupo de Estado Slido, Instituto de Fsica, Facultad de Ciencias Exactas y Naturales,
Universidade de Antioquia UdeA, Calle 70 No 52-21, Medellin, Colombia
bGroup of Ferroic Material, Physics Department, Federal University of So Carlos.

Rod. Washington Luiz, km 235. Cep: 13565905 So Carlos-SP Brasil

Abstract

Ferroelectric ceramic of 0.5% Er3+ doped and un-doped (1-x)[Pb(1-y)Lay(Mg1/3Nb2/3)O3]-xPbTiO3 (PLMN-PT) were
prepared by solid state reaction using the columbite method and densified by conventional sintering (CS), uniaxial hot
pressing (HP) and spark plasma sintering (SPS). In this work, we reviewed and discussed the influences of
densification process on microstructural, structural and dielectric properties of the ceramics. It was observed that fully
compacted specimens were obtained without porosity and homogeneous microstructure. Density of ceramics close to
theoretical value (more than 99%) could be reached easily by HP. Heat treatment process in ceramics obtained by SPS
eliminates the dark colour and improves transparency. Also, its reviewed and discussed the influences of densification
process on microstructural, structural properties of the ceramics, finding the electrical properties are favoured by HP.

2014 The Authors. Published by Elsevier B.V.


Selection and peer-review under responsibility of Elhadi M. Shakshuki.

Keywords:PLMN-PT, Microstructural, Structural, Dielectric, Densified.

2014 The Authors. Published by Elsevier B.V.


Selection and peer-review under responsibility of Elhadi M. Shakshuki.
2

1. Introduction

Lead magnesium niobate Pb(Mg1/3Nb2/3)O3 (PMN) was discovered by Smolenskii and Agranovskaya while studying
a large number of perovskite type compounds1. The PMN belongs to the family of complex perovskites, being an
important relaxor ferroelectric material with diffuse phase transition, high values of electrostatic coefficients and giant
dielectric constant value2. It is also known that the dielectric properties of PMN can be further enhanced by additions
of PbTiO3, thus making the PMN-PbTiO3 (PMN-PT) system a promising material for their potential applications in
multilayer capacitor, actuator, electro-optical modulator, ultrasonic transducer and infrared detector due to their
excellent dielectric, piezoelectric, electro-optic, electrostrive and pyroelectric properties3,4,5,6.

It is known that the addition of La3+ allows to enhance optical and electrooptic properties7 and stabilizes the structure
PMN-PT as a function of temperature, an important parameter for the manufacture of electronic devices8.

However, these importance properties are strongly depending on the purity of the raw materials, method of preparation
and densification, since they can be limited by the formation of the unwanted pyrochlore phases with poor electrical
properties upon processing. Over the years, considerable efforts with various preparation techniques have been
proposed and used to fabricate pyrochlore-free PMN-PT ceramics. Among these, the columbite method, in which
prefabricated MgNb2O6 is reacted with an appropriate proportion of PbO, has been widely used in the synthesized of
phase-pure perovskite PMN-based ceramics9.

There are different methods to densified ceramics which include uniaxial Hot pressing (HP), conventional sintering
(CS), and Spark plasma sintering (SPS). The (HP) sintering is a high-pressure low-strain-rate powder metallurgy
process for forming of a powder or powder compact at a temperature high enough to induce sintering and creep
processes. This is achieved by the simultaneous application of heat and pressure. Densification at high pressure works
through particle rearrangement and plastic flow at the particle contacts10. The (CS), simply heating the material for a
long period of time and the SPS method combining mechanical pressure and an electric energy in a pulse shape as the
heat source for sintering, this allows to reduce time and temperature in densification11,12. The latter method being little
studied in the influence of the physical properties of the ferroelectric ceramics. However, the influence of this method
on the physical properties of ferroelectric ceramics has not yet been understood. In this work, we reviewed and
discussed the influences of densification process on microstructural, structural and dielectric properties PLMN-PT
and PLMN-PT:0.5Er ceramics which has not yet performed.

2. Experimental Procedure

The powder was synthesized by the columbite or two-stage calcining method9. The batch formulae were (0.87)[Pb(1-
y)Lay(Mg1/3Nb2/3)O3]-0.13PbTiO3, with y=0.01 and doped with 0.5% in weight of Er2O3.

The starting materials were Lanthanum Oxide, La2O3 (Aldrich, >99% purity), Niobium Oxide, Nb2O5 (Alfa Aesar
99.9+% purity), Magnesium Carbonate Hydroxide Pentahydrate, (MgCO3)4.Mg(OH)2.5H2O (Aldrich 99% purity),
Lead Oxide, PbO (MGK 99%), Titanium Oxide, TiO2 (Alfa Aesar, 99.8% purity), Neodymium (III) Oxide,
Nd2O3(Aldrich, 99.99% purity), Erbium (III) Oxide and Er2O3(Aldrich, >99.99% purity). The
(MgCO3)4.Mg(OH)2.5H2O was carried up to 1100o C, for 4h, to drive off CO2 and H2O and obtain the correct amount
of MgO for a stoichiometric reaction with Nb2O5. In the first stage, MgO and Nb2O5 powders were ball-milled and
prereacted at 1100o C for 4 h, in air, to form the columbite phase (MgNb2O6). In the second stage, the synthesized
(MgNb2O6) (MN) was ball-milled in isopropanol, for 24 h, with appropriate amounts of PbO, TiO2, La2O3, Er2O3 and
heated at 900o C, for 4h, in oxygen atmosphere, at a controlled pressure of 200 kPa. The calcined powders were
pressed into pellets 14 mm in diameter and 10 mm in thickness with the addition of an appropriate amount of polyvinyl
alcohol (PVA) binder. The pellets were sintered in hot uniaxial pressing in O2 atmosphere followed for 4 h at 1260o
3

C, and 6 MPa, Spark Plasma Sintering for 10 min at 980o C , and 2 MPa and convencional sintering for 13h at 1260o
C in O2 atmosphere.

The phases and the structural parameters were determined by X-ray diffraction (XRD) using a Rigaku diffractometer,
with CuK radiation. The measures were performed at room temperature. The lattice parameters were calculated by
least squares from the positions of the diffraction peaks. Apparent densities were determined by the Archimedes
method. The microstructural features of the samples were investigated by scanning electron microscopy (SEM), using
a Jeol JSM 5800 LV. For dielectric measurement, gold electrodes were deposited on both faces of the disk samples (5
mm diameter and ~1.0 mm thick). The relative permittivity, was measured by impedance analysis (HP4194A).

3. Results and discussion

3.1 Phase Structure

In Fig.1 shows the x-ray diffraction pattern of calcined PLMN-13PT and PLMN-13:0.5Er powders, where can be
observed majority perovskite pseudo-cubic phase13,14 and secondary pyrochlore phase Pb1.83(Mg0.29Nb1.71)O6.39 was
also observed. The addition of Erbium causes a shift to a smaller angle of the peak [111]. This is because the Erbium
occupies the A-site for possible replacements of (Pb/La) in the PLMN-PT structure3. However, the ionic radius of
La3+ and Pb2+ (1.032nm and 1.19nm respectively) are smaller than the radius of Er3+ (0.86nm), so this occupation
leads to lattice distortion and an increase in interplanar space d. According to the Bragg equation sin( ) = /2,
when d increases, theta will decrease, which means that the peak shifts to smaller angles.

Fig. 1 XRD patterns of PLMN-13PT and PLMN-13PT:0.5Er powder.


4

The Fig. 2 (a) and (b) shows the x-ray diffraction pattern of PLMN-13PT and PLMN-13PT:0.5Er ceramics densified
for different methods respectively. In all the samples a perovskite phase formation with rhombohedral symmetry
(pseudo-cubic)14 and undesired pyrochlore phase remains. The relative content of the pyrochlore phase are shown in
the Table 1, and were calculated kpyro ( %), using an approximate equation:


=
+

Where and were the integral intensity of [110] perovskite diffraction peak and the [222] pyrochlore
diffraction peak, respectively15. The values obtained show that the HP method decreases the undesired phase due to

the O2 atmosphere control16, in addition, a lower pyrochlore phase value is present and independent of the densification
process in the non-doped PLMN-PT ceramics in relation to ceramics doped.
The samples obtained by SPS were dark gray because of oxygen deficiency in the crystal lattices17. A heat treatment
in an atmosphere rich in lead and O2 (SPSTT) causes an oxidation in the material and allowing changes the color of
the samples to yellow18 but these changes are not shown in the structural properties of this work.

Fig. 2 a). XRD patterns of PLMN-13PT ceramics in function of densified process; (b) XRD patterns of PLMN-13PT:0.5Er
ceramics in function of densified process.

3.2 Density and Microstructure

The cell parameters and relative densities of PLMN-13PT and PLMN-13PT:0.5Er ceramics in function of densified
process are shown in Table 1. Cell parameters were calculated from the XRD results and bulk density was measured
using Archimedes Method. The relative densities of the densified samples for HP are greater than 99% of the
5

theoretical density. For samples densified by other methods are achieved a lower percentage than those densified by
HP, but higher than 91%, which is according to the majority of the data obtained by several researchers Santos19,
Guerra20, Kim21.

Table1. Cell parameters, density and relative content of the pyrochlore phase on PLMN-PT and PLMN-PT:0.5Er ceramics in
function of densified process.

Cell Bulk Relative kpyro


Sample Parameters density(g/cm3) density (%)
(A) (%)
CS PLMN-13PT 4.014 7.706 94.1 17
CS PLMN-13PT:Er 4.033 7.668 96 11
HP PLMN-13PT 4.023 8.060 99 7
HP PLMN-13PT:Er 4.038 8.077 99.4 6
SPS PLMN-13PT 4.038 7.438 93 11
SPS PLMN-13PT:Er 4.040 7.705 96.3 10
SPSTT PLMN-13PT 4.046 7.270 91 13
SPSTT PLMN13PT:Er 4.045 * ** 10

The specimens prepared by SPS and after subjected to heat treatment SPSTT, their density is slightly decreased as
observed by Park22, this could be due to an increase of the cell parameters.

The fractured surfaces of PLMN-PT and PLMN-PT:0.5Er ceramics are shown in Fig 3. The PLMN-PT ceramics (Fig
3a, 3c, 3e) exhibit transgranular fracture, which could be attributed to the low content of lanthanum (0.01% weight).
According to Winters research23 PMN-PT ceramic shows transgranular fracture character without La3+ doping, while
intergranular fracture character occurs gradually with increase of La3+ content24. In contrast, PLMN-PT ceramics
doped with Erbium (Fig 3b, 3d, 3f) mainly present an intergranular fracture. This was due to the replacement of
(Pb2+/La3+) by Er3+ causing possibly the migration of these to the grain boundary, which produces a weaker phase. It
can also be observed that the fractured surface for each material presented similar microstructure without porosity and
are independent of densification process.
It is known the grain size of samples densified by HP and CS is larger than those densified by SPS, and this can be
observed in the sample PLMN-PT:0.5% Er in (Fig 3b, 3d, 3f).

*Due to the dimensions of the sample, it was not possible to take density measurements.
6

Fig. 3. Fracture surface of (a) PLMN-13PT densified by CS; (b) PLMN-13PT:0.5Er densified by CS; (c) PLMN-13PT densified
by HP; (d) PLMN-13PT:0.5Er densified by HP; (e) PLMN-13PT densified by SPS; (f) PLMN-13PT:0.5Er densified by SPS.

3.3 Dielectric Properties

The permittivity (real ' and imaginary ") was measured at various temperatures in the frequency range 1kHz - 1MHz.
All the samples exhibit typical relaxor behavior 21,25, with the magnitude of ' decreasing with increasing frequency,
and the maximum permittivity real 'max shifting to higher temperatures, as shown in Fig 4. The variation of permittivity
' peak in function of temperature can be directly related to the diffuseness coefficient that indicates the degree of
the diffuse phase transition and indicates the character of the phase transition, which were calculated from empirical
formula of Santos Eiras26; for experimental measurements performed at 1 kHz and the results are shown in Table 2.
7

Table2. Dielectric properties of PLMN-PT and PLMN-PT:0.5Er ceramics and dielectric loss factor Tan in function of densified
process to 1KHz.

'max Tmax(K) Tan


Sample
CS PLMN-13PT 16913 313 52.52 1.68 0.62
CS PLMN-13PT:Er 14910 309 62.44 1.66 0.08
HP PLMN-13PT 13743 307 54.00 1.62 0.14
HP PLMN-13PT:Er 16404 309 55.5 1.69 0.68
SPSTT PLMN-13PT 5501 310 100.01 1.99 1.40
SPSTT PLMN-13PT:Er 7445 336 93.8 2.00 1.20

The values of confirm a relaxor behaviour in the samples densified by HP and CS being this type of transition
attributed to the formation of polar clusters that begin to interact in higher temperatures to Tmax26, while samples
densified by SPS method present a complete diffuse phase transition12 due to the non-interaction of polar clusters
formed at higher temperatures to Tmax.. Also, that is related to the dielectric permittivity peak broadening, indicates
large fluctuations in composition and structural disorder27,28, this is possibly due to the rapid densification in SPS
process, which does not allow a rearrangement of the ions in the crystalline structure, thus causing greater fluctuations
in the composition. Therefore, these parameters demonstrate a degraded in the dielectric properties of the material. In
addition, the small grain size of the samples shown above, increases the fraction of the grain boundary phase which
contributes to the decrease of the maximum permittivity 'max.
The values of dielectric loss factor, Tan indicates greater contribution of the imaginary part " in ceramics obtained
by SPS.

4. Conclusion

Fully compacted specimens were obtained without porosity and homogeneous microstructure independent of method
of densified process. Density of ceramics close to theorical value (more that 99%) could be reached easily by HP. The
type fracture of the ceramic systems is independent of the densification process. Lower pyrochlore phase value is
present and independent of the densification process in the non-doped PLMN-PT ceramics in relation to the ceramics
doped. The rapid densification process in samples obtained by SPS, does not allow a rearrangement of the ions in the
crystalline structure, thus causing greater fluctuations in the composition and a complete diffuse phase transition due
to the non-interaction of polar clusters formed at higher temperatures to Tmax..

5. Acknowledgements

This research was partially supported by Colombian Agencies: CODI-Universidad de Antioquia (Estrategia de
Sostenibilidad 2016-2018 de la Universidad de Antioquia and project: ''Sntesis y caracterizacin de cermicas
transparentes multifuncionales para aplicaciones en dispositivos electro-pticos y para la construccin de matrices
para lser de estado slido''), Facultad de Ciencias Exactas y Naturales-Universidad de Antioquia and to CAPES,
FAPESP and CNPq for thefinancial support. And to Mr. Francisco Jos Picon and Natalia Zanardi for the technical
support.
8

Fig 4. Dielectric measured (a) PLMN-13PT densified by CS; (b) PLMN-13PT:0.5Er densified by CS; (c) PLMN-13PT densified
by HP; (d) PLMN-13PT:0.5Er densified HP; (f) PLMN-13PT densified by SPS; (f) PLMN-13PT:0.5Er SPS.
9

6. References

1. Francis S. Galasso, R. S. and N. K. Structure, properties and preparation of perovskite. (1969).


2. Kenji, U. Ferroelectric devices. Marcel Derker Inc., New York (2000).
3. Wei, Z. et al. Optical characteristics of Er3+-doped PMNPT transparent ceramics. Ceram. Int. 38, 3397
3402 (2012).
4. Shannigrahi, S. & Yao, K. Thermal annealing effects on the structural and electrical properties of PMN-PZ-
PT ternary thin films deposited by a sol-gel process. J. Eur. Ceram. Soc. 25, 759765 (2005).
5. Haertling, G. H. Ferroelectric Ceramics: History and Technology. J. Am. Ceram. Soc. 82, 797818 (1999).
6. Suzuki, a, Ishii, T. & Maruyama, Y. Optical switching in polymer gels. J. Appl. Phys. 80, 131 (1996).
7. Sabat, R. G. (2012). Characterization of PLZT Ceramics for Optical Sensor and Actuator Devices. INTECH
Open Access Publisher.
8. Jiang, H., Zou, Y. K., Chen, Q., Li, K. K., Zhang, R., Wang, Y., ... & Zheng, Z. (2005, January).
Transparent electro-optic ceramics and devices. In Photonics Asia 2004 (pp. 380-394). International Society
for Optics and Photonics.
9. Swartz, S. L. & Shrout, T. R. Fabrication of perovskite lead magnesium niobate. Mater. Res. Bull. 17, 1245
1250 (1982).
10. Wang, S. F. et al. Transparent ceramics: Processing, materials and applications. Prog. Solid State Chem. 41,
2054 (2013).
11. Noudem, J. G., Prevel, M., Veres, A., Chateigner, D. & Galy, J. Thermoelectric Ca3Co4O9 ceramics
consolidated by Spark Plasma sintering. J. Electroceramics 22, 9197 (2009).
12. Zuo, R., Granzow, T., Lupascu, D. C. & Rodel, J. PMN-PT ceramics prepared by spark plasma sintering. J.
Am. Ceram. Soc. 90, 11011106 (2007).
13. Londoo, F. A., Eiras, J. A. & Garcia, D. Novas cermicas ferroeltricas transparentes com altos
coeficientes eletropticos: PLMN-PT. Cermica 57, 404408 (2011).
14. Andrs, F., Badillo, L., Eiras, J. A., Milton, F. P. & Garcia, D. Preparation and Microstructural , Structural ,
Optical and Electro-Optical Properties of La Doped PMN-PT Transparent Ceramics. 2012, 157162 (2012).
15. Fang, B., Ding, C., Wu, J., Du, Q. & Ding, J. pss. 1645, 16411645 (2011).
16. I, C. F. A. L. et al. EFFECT OF ATMOSPHERE ON THE PEROVSKITE. XXIV, 1926 (2012).
17. Zhang, B., Zhang, L., Li, J., Zhang, H. & Jin, S. SPS Sintering of NaNbO 3 -KNbO 3 Piezoelectric
Ceramics. 479, 11651168 (2005).
18. Singh, A. K., Pandey, D., & Zaharko, O. (2006). Powder neutron diffraction study of phase transitions in
and a phase diagram of (1 x)[Pb (Mg 1 3 Nb 2 3) O 3] x Pb Ti O 3. Physical Review B, 74(2), 024101
19. Santos, I. a. et al. Cermicas ferroeltricas transparentes de PLZT e PLMN-PT: processamento e
propriedades. Cermica 49, 9298 (2003).
20. Guerra*, J. D. S., Souza, J. A., Garcia, D. & Eiras, J. A. Non-Linear Dielectric Properties of PLMN-PT
Relaxor Ferroelectrics. Ferroelectrics 369, 170178 (2008).
21. Kim, N., Mchenry, D. A., Jang, S. & Shrout, T. R. Fabrication of Optically Transparent lead Magnesium
Niobate Polycrystalline Ceramics Using Hot Isostatic Pressing. J. Am. Ceram. Soc. 73, 923928 (1989).
22. Park, J., Chung, U., Hwang, N. M. & Kim, D. Preparation of Lead Magnesium niobate -Lead titanate
ceramics by SPS. J. Am. Ceram. 84, 30573059 (2001).
23. Winter, M. R., Pilgrim, S. M., & Lejeune, M. (2001). Study on the Effects of Lanthanum Doping on the
Microstructure and Dielectric Properties of 0.9 Pb (Mg1/3Nb2/3) O30.1 PbTiO3. Journal of the American
Ceramic Society, 84(2), 314-20.
24. Song, Z. et al. Fabrication and ferroelectric/dielectric properties of La-doped PMN-PT ceramics with high
optical transmittance. Ceram. Int. 43, 37203725 (2017).
25. T Cross, L. E. (1987). Relaxor ferroelectrics. Ferroelectrics, 76(1), 241-267.
26. Santos, I. a & Eiras, J. a. Phenomenological description of the diffuse phase transition in ferroelectrics. J.
Phys. Condens. Matter 13, 1173311740 (2001).
27. Badapanda, T. Dielectric Behavior of Yttrium doped Barium-zirconium-titanate Ceramics. 55, 749754
10

(2009).
28. Isupov, V. A. Ferroelectric and Antiferroelectric Perovskites PbB 0.5 B 0.5 O 3. Ferroelectrics 289,
(2003).
Influence of densification process on structural, microstructural
and dielectric properties of PLMN-PT:0.5%Er

Ferroelectric ceramic of 0.5% Er3+ doped and no-doped (1-x)[Pb(1-y)Lay(Mg1/3Nb2/3)O3]-


xPbTiO3 (PLMN-PT) were prepared by solid state reaction using the columbite method and
densified by conventional sintering (CS), uniaxial hot pressing (HP) and spark plasma
sintering (SPS).
We reviewed and discussed the influences of densification process on microstructural,
structural and dielectric properties of the ceramics
Heat treatment process in ceramics obtained by SPS eliminates the dark colour and
improves transparency
The ceramics exhibits relaxor behavior.
XRD analysis confirms the formation of perovskite phase and two pyrochlore
phases in all the samples.