Research ArticleStructure and Physical Properties of PZT-PMnN-PSNCeramics Near the Morphological Phase Boundary
Nguyen Dinh Tung Luan1 Le Dai Vuong12 Truong Van Chuong2
and Nguyen Truong Tho2
1 The Fundamental Science Department Hue Industry College Hue City Vietnam2Department of Physics College of Sciences Hue University Hue City Vietnam
Correspondence should be addressed to Nguyen Dinh Tung Luan ntungluanyahoocom
Received 1 August 2013 Accepted 11 December 2013 Published 20 January 2014
Academic Editor Mohammad Mahroof-Tahir
Copyright copy 2014 Nguyen Dinh Tung Luan et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited
The 09Pb(ZrxTi1minusx)O3-007Pb(Mn13Nb23)O3-003Pb(Sb
12Nb12)O3(PZT-PMnN-PSN) ceramics were prepared by columbite
method The phase structure of the ceramic samples was analyzed Results show that the pure perovskite phase is in all ceramicsspecimensThe effect of the ZrTi ratio on the region of morphotropic phase boundary for PZT-PMnN-PSN ceramics was studiedExperimental results show that the phase structure of ceramics changes from tetragonal to rhombohedral with the increase ofthe content of ZrTi ratio in the system The composition of PZT-PMnN-PSN ceramics near the morphotropic phase boundaryobtained is the ratio of ZrTi 4951 At this ratio the ceramic has the optimal electromechanical properties the 119896
119901= 061 the
120576max = 29520 the 11988931 = minus236 pCN the 119876119898 = 2400 high remanent polarization (119875119903= 492 120583Csdotcmminus2) and low coercive field
119864119888= 1028 kVsdotcmminus1
1 Introduction
Lead zirconate titanate (PZT) is one of the most commonlyused ferroelectric ceramic materials The material has beenstudied intensively since discovery of the miscibility oflead titanate and lead zirconate in the 1950s [1ndash5] Due totheir excellent dielectric pyroelectric piezoelectric andelectrooptic properties they have a variety of applicationsin high energy capacitors nonvolatile memories (FRAM)ultrasonic sensors infrared detectors electrooptic devicesand step-down multilayer piezoelectric transformers for AC-DC converter applications [5 6] Until now many ternaryand quaternary systems such as Pb(Ni
13Nb23
)O3-PZT
Pb(Y23
W13
)O3-PZT Pb(Mn
13Sb23
)O3-PZT Pb(Mg
13
Nb23)O3-Pb(Ni
13Nb23)O3-PZT Pb(Ni
12W12)O3-Pb(Mn
13
Nb23
)O3-PZT and PZT-PMnSbN [4 5 7ndash11] have been
synthesized by modifications or substitutions to satisfy
the requirements of practical applications of piezoelectrictransformer
In ceramicsmanufacturing technology piezoelectric PZTsystem ceramics compositions aremostly near the tetragonal-rhombohedral (T-R) morphotropic phase boundary (MPB)The electromechanical response of these ceramics is known tobe most pronounced at the MPB So there have been manyinvestigations on the coexistence of two phases near MPB inPZT system [3]The reports suggested the existence of a rangeof compositions where both tetragonal and rhombohedralphases are thermodynamically stable [7 12]
In this study 09Pb(ZrxTi1minusx)O3-007Pb(Mn13
Nb23
)O3-003Pb(Sb
12Nb12
)O3(PZT-PMnN-PSN)ceramics in the
vicinity ofMPBwere investigated according to the ZrTi ratiocontent The purpose of this work is to study structure andferroelectric and piezoelectric properties in the vicinity ofthe MPB in detail Furthermore the width of coexistence of
Hindawi Publishing CorporationAdvances in Materials Science and EngineeringVolume 2014 Article ID 821404 8 pageshttpdxdoiorg1011552014821404
Figure 2 Variations of relative content of the tetragonal andrhombohedra phases with ZrTi ratio
tetragonal and rhombohedra phases and the exact compo-sition of the MPB in chemically homogeneous PZT-PMnN-PSN ceramics were determined
2 Experimentals
The polycrystalline samples of PZT-PMnN-PSN were syn-thesized by columbite precursor method The raw materialsincluding powders (high purity) of PbO (99) ZrO
2(999)
TiO2(99) MnCO
3(99) Sb
2O3(99) and Nb
2O5
(999) for the given composition were weighted by moleratio First the finely mixed powder of MnCO
3and Nb
2O5
Sb2O3and Nb
2O5are mixed in a Teflon-mortar for about
10 h in an acetone medium and then calcined at 1200∘C inan alumina crucible for 3 h The calcined powder was thengrinded andmixed bymortar againwith PbO ZrO
2andTiO
2
for 30 h The finely mixed powder was calcined at 850∘C for2 h
The ground materials were pressed into disk 12mmin diameter and 15mm in thickness under 100MPa Thesamples were sintered in a sealed alumina crucible withPbZrO
3coated powder at temperature 1150∘C for 2 h
Scanning electron micrograph of the sample was taken atroom temperature The sintered pellet was polished andsilver electroded and connected to an LCR meter (HiokiJapan) for dielectric measurement The frequency depen-dence of dielectric constant and loss tangent were obtainedusing the LCR meter in the frequency range from 01 kHzto 500 kHz The polarization-electric field (P-E) hystere-sis loops were measured by a Sawyer-Tower circuit at50Hz
As-sintered samples were ground and polished to removethe surface layer for X-ray diffraction (XRD DMAX-RBRigaku Japan) CuK120572 radiationwith a step of 001 s was usedThe microstructure of the samples was examined by using ascanning electron microscope (SEM)The electromechanicalcoupling factor (119896
119901) mechanical quality factor (119876
119898) and
piezoelectric coefficient (11988931) were calculated by using the
resonance-antiresonance method The dielectric constant
was calculated from the capacitance and the dimension of thesamples
3 Results and Discussion
31 Structure and Microstructure It is reported that tetrag-onal rhombohedra and T-R phases were identified by ananalysis of the peaks (002 (tetragonal) 200 (tetragonal) and200 (rhombohedra)) in the 2120579 range 43∘ndash47∘ The splitting of(002) and (200) peaks indicates that they are the ferroelectrictetragonal phase (FT) while the single (200) peak showsthe ferroelectric rhombohedra phase (FR) [1 6 13] Figure 1shows the XRD patterns of PZT-PMnN-PSNwith ZrTi ratioat 5446 up to 4654 Triplet peaks indicate that the samplesconsist of a mixture of tetragonal and rhombohedra phases
A transition from tetragonal phase to rhombohedra phaseis observed as ZrTi ratio increases The multiple peakseparation method was used to estimate the relative fractionof coexisting phases The relative phase fraction was thencalculated by the following equations [14]
With increasing ZrTi ratio tetragonal relative fractiondecreases and rhombohedra relative fraction increases Theanalysis of the relative phase fraction in the PZT-PMnN-PSNsystem indicates that tetragonal and rhombohedra phasescoexist in the composition range for 048 le 119909 le 052 as shownin Figure 2
Figure 3 shows the SEM image of the fractured surfaceof PZT-PMnN-PSN ceramics at different ZrTi ratios It isobserved from the micrographs that the average grain size ofsamples are increased with the increasing amount of ZrTiratio However when further increasing the ZrTi ratio to5149 the average grain size is reduced These results are ingood agreement with the reported in the literature [15]
32 Dielectric and Ferroelectric Properties
321 The Influence of ZrTi Ratio on the Dielectric PropertiesFigure 4 shows the temperature dependence of dielectricpermittivity and dielectric loss tan 120575 of PZT-PMnN-PSNsystem (1 kHz) with ZrTi ratios 4654 up to 5446 respec-tively As shown in Figure 4 all the samples in morphotropicphase boundary region (ZrTi = 4852minus5248) exhibit typ-ical relaxor ferroelectric behavior around The dielectricresponses are characterized by diffuse dielectric peaks anda slight shift of permittivity of maximum toward highertemperature with increasing frequencies
By comparing the curves in Figure 1 we see that thebroadness of dielectric response increases with an increase inZrTi ratio and the largest is at ZrTi = 4951 The tempera-ture of dielectric permittivity maximum also increases withincrease of ZrTi ratio All samples have a temperature called
4 Advances in Materials Science and Engineering
MZ46 MZ47
MZ48 MZ49
MZ50 MZ51
MZ52 MZ53
Figure 3 Surface morphologies observed by SEM of PZT-PMnN-PSN ceramics at various ratios of ZrTi
Burn temperature at which dielectric response starts comply-ing Curie-Weiss law and the system starts the transition intoparaelectric phase
Figure 5 shows Curie-Weiss dependence of the permit-tivity of the samples at temperatures start to 119879
119861 The fitting
parameters [14] are given in Table 1From Table 1 we can see that all the temperature values
extend to decrease with the increase of ZrTi ratio
322 The Influence of ZrTi Ratio on the Ferroelectric Proper-ties Figure 6 shows 119875-119864 hysteresis loops of all samples Thewell-saturated hysteresis loops were observed and the values
of remanent polarization (119875119903) and coercive field (119864
119888) were
presented in Table 2Itrsquos demonstrated that the hysteresis loops of all samples
are of typical forms characterizing ferroelectric materialsThe remanent polarization (119875
119903) reaches the maximum value
of 492 120583Ccm2 and The coercive field (119864119888) reaches the
minimum value of 1028 kVsdotcmminus1 at ZrTi = 4951 (Figure 7)
4 Piezoelectric Properties
Figure 8 shows the piezoelectric and dielectric propertiesas a function of ZrTi ratio PZT-PMnN-PSN exhibits high
Advances in Materials Science and Engineering 5
100 150 200 250 300 350 400 4500
5000
10000
15000
20000
25000
30000
M046M047
M048
M049M050
M051
M052M053
M054120576
T (∘C)
(a)
50 100 150 200 250 300 350 400 450000
005
010
015
M046
M047
M048
M049M051
M050M052
M053
M054
T (∘C)
tan120575
(b)
Figure 4 (a) Dielectric constant and (b) loss tangent of PZT-PMnN-PSN at various ZrTi ratios
200 250 300 350 400 45000
200 250 300 350 400 45
Experimental dataFitting linear
M046 M047 M048
M049 M050
M052
M051
M053 M054
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
Figure 5 Curie-Weiss dependence of the permittivity of the samples at temperatures start to 119879119861
6 Advances in Materials Science and Engineering
0 10 20 30 40 50 60
0
20
40
60
80
0 10101010100101001010100001010011 20 30 400
0
2000002000202020000020002
M046 M047 M048
M049 M050 M051
M052 M053 M054
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
Figure 6 119875-119864 hysteresis loops of PZT-PMnN-PSN samples
Table 1 Dielectric properties and fitting parameters of PZT-PMnN-PSN ceramics
piezoelectric coefficient and electromechanical coupling fac-tor around the MPB From the trend of the variation ofpiezoelectricity it reaches the maximum values of 119889
Simple diagram phase of PZT-PMnN-PSN ceramicsnear MPB which is attractive system displaying excellentpiezoelectric and dielectric properties good electrostrictiveeffects and relaxation of ferroelectric phase transition isshown in Figure 9
Advances in Materials Science and Engineering 7
10
11
12
13
14
046 048 050 052 05416
20
24
28
32
36
40
44
48
52
x = Zr(Zr + Ti)
Pr
(120583C
cm2)
Pr
Ec
Ec
(kV
cm
)
Figure 7 The 119875119903and the 119864
119888as a function of ZrTi ratios
2200
2400
2600
2800
3000
3200
3400
040
045
050
055
060
065
070
45 46 47 48 49 50 51 52 53 54 55100
120
140
160
180
200
220
240
T RMPB
x = Zr(Zr + Ti)
Qm
Qm
kp
kp
minusd31
minusd31
(pC
N)
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
Figure 2 Variations of relative content of the tetragonal andrhombohedra phases with ZrTi ratio
tetragonal and rhombohedra phases and the exact compo-sition of the MPB in chemically homogeneous PZT-PMnN-PSN ceramics were determined
2 Experimentals
The polycrystalline samples of PZT-PMnN-PSN were syn-thesized by columbite precursor method The raw materialsincluding powders (high purity) of PbO (99) ZrO
2(999)
TiO2(99) MnCO
3(99) Sb
2O3(99) and Nb
2O5
(999) for the given composition were weighted by moleratio First the finely mixed powder of MnCO
3and Nb
2O5
Sb2O3and Nb
2O5are mixed in a Teflon-mortar for about
10 h in an acetone medium and then calcined at 1200∘C inan alumina crucible for 3 h The calcined powder was thengrinded andmixed bymortar againwith PbO ZrO
2andTiO
2
for 30 h The finely mixed powder was calcined at 850∘C for2 h
The ground materials were pressed into disk 12mmin diameter and 15mm in thickness under 100MPa Thesamples were sintered in a sealed alumina crucible withPbZrO
3coated powder at temperature 1150∘C for 2 h
Scanning electron micrograph of the sample was taken atroom temperature The sintered pellet was polished andsilver electroded and connected to an LCR meter (HiokiJapan) for dielectric measurement The frequency depen-dence of dielectric constant and loss tangent were obtainedusing the LCR meter in the frequency range from 01 kHzto 500 kHz The polarization-electric field (P-E) hystere-sis loops were measured by a Sawyer-Tower circuit at50Hz
As-sintered samples were ground and polished to removethe surface layer for X-ray diffraction (XRD DMAX-RBRigaku Japan) CuK120572 radiationwith a step of 001 s was usedThe microstructure of the samples was examined by using ascanning electron microscope (SEM)The electromechanicalcoupling factor (119896
119901) mechanical quality factor (119876
119898) and
piezoelectric coefficient (11988931) were calculated by using the
resonance-antiresonance method The dielectric constant
was calculated from the capacitance and the dimension of thesamples
3 Results and Discussion
31 Structure and Microstructure It is reported that tetrag-onal rhombohedra and T-R phases were identified by ananalysis of the peaks (002 (tetragonal) 200 (tetragonal) and200 (rhombohedra)) in the 2120579 range 43∘ndash47∘ The splitting of(002) and (200) peaks indicates that they are the ferroelectrictetragonal phase (FT) while the single (200) peak showsthe ferroelectric rhombohedra phase (FR) [1 6 13] Figure 1shows the XRD patterns of PZT-PMnN-PSNwith ZrTi ratioat 5446 up to 4654 Triplet peaks indicate that the samplesconsist of a mixture of tetragonal and rhombohedra phases
A transition from tetragonal phase to rhombohedra phaseis observed as ZrTi ratio increases The multiple peakseparation method was used to estimate the relative fractionof coexisting phases The relative phase fraction was thencalculated by the following equations [14]
With increasing ZrTi ratio tetragonal relative fractiondecreases and rhombohedra relative fraction increases Theanalysis of the relative phase fraction in the PZT-PMnN-PSNsystem indicates that tetragonal and rhombohedra phasescoexist in the composition range for 048 le 119909 le 052 as shownin Figure 2
Figure 3 shows the SEM image of the fractured surfaceof PZT-PMnN-PSN ceramics at different ZrTi ratios It isobserved from the micrographs that the average grain size ofsamples are increased with the increasing amount of ZrTiratio However when further increasing the ZrTi ratio to5149 the average grain size is reduced These results are ingood agreement with the reported in the literature [15]
32 Dielectric and Ferroelectric Properties
321 The Influence of ZrTi Ratio on the Dielectric PropertiesFigure 4 shows the temperature dependence of dielectricpermittivity and dielectric loss tan 120575 of PZT-PMnN-PSNsystem (1 kHz) with ZrTi ratios 4654 up to 5446 respec-tively As shown in Figure 4 all the samples in morphotropicphase boundary region (ZrTi = 4852minus5248) exhibit typ-ical relaxor ferroelectric behavior around The dielectricresponses are characterized by diffuse dielectric peaks anda slight shift of permittivity of maximum toward highertemperature with increasing frequencies
By comparing the curves in Figure 1 we see that thebroadness of dielectric response increases with an increase inZrTi ratio and the largest is at ZrTi = 4951 The tempera-ture of dielectric permittivity maximum also increases withincrease of ZrTi ratio All samples have a temperature called
4 Advances in Materials Science and Engineering
MZ46 MZ47
MZ48 MZ49
MZ50 MZ51
MZ52 MZ53
Figure 3 Surface morphologies observed by SEM of PZT-PMnN-PSN ceramics at various ratios of ZrTi
Burn temperature at which dielectric response starts comply-ing Curie-Weiss law and the system starts the transition intoparaelectric phase
Figure 5 shows Curie-Weiss dependence of the permit-tivity of the samples at temperatures start to 119879
119861 The fitting
parameters [14] are given in Table 1From Table 1 we can see that all the temperature values
extend to decrease with the increase of ZrTi ratio
322 The Influence of ZrTi Ratio on the Ferroelectric Proper-ties Figure 6 shows 119875-119864 hysteresis loops of all samples Thewell-saturated hysteresis loops were observed and the values
of remanent polarization (119875119903) and coercive field (119864
119888) were
presented in Table 2Itrsquos demonstrated that the hysteresis loops of all samples
are of typical forms characterizing ferroelectric materialsThe remanent polarization (119875
119903) reaches the maximum value
of 492 120583Ccm2 and The coercive field (119864119888) reaches the
minimum value of 1028 kVsdotcmminus1 at ZrTi = 4951 (Figure 7)
4 Piezoelectric Properties
Figure 8 shows the piezoelectric and dielectric propertiesas a function of ZrTi ratio PZT-PMnN-PSN exhibits high
Advances in Materials Science and Engineering 5
100 150 200 250 300 350 400 4500
5000
10000
15000
20000
25000
30000
M046M047
M048
M049M050
M051
M052M053
M054120576
T (∘C)
(a)
50 100 150 200 250 300 350 400 450000
005
010
015
M046
M047
M048
M049M051
M050M052
M053
M054
T (∘C)
tan120575
(b)
Figure 4 (a) Dielectric constant and (b) loss tangent of PZT-PMnN-PSN at various ZrTi ratios
200 250 300 350 400 45000
200 250 300 350 400 45
Experimental dataFitting linear
M046 M047 M048
M049 M050
M052
M051
M053 M054
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
Figure 5 Curie-Weiss dependence of the permittivity of the samples at temperatures start to 119879119861
6 Advances in Materials Science and Engineering
0 10 20 30 40 50 60
0
20
40
60
80
0 10101010100101001010100001010011 20 30 400
0
2000002000202020000020002
M046 M047 M048
M049 M050 M051
M052 M053 M054
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
Figure 6 119875-119864 hysteresis loops of PZT-PMnN-PSN samples
Table 1 Dielectric properties and fitting parameters of PZT-PMnN-PSN ceramics
piezoelectric coefficient and electromechanical coupling fac-tor around the MPB From the trend of the variation ofpiezoelectricity it reaches the maximum values of 119889
Simple diagram phase of PZT-PMnN-PSN ceramicsnear MPB which is attractive system displaying excellentpiezoelectric and dielectric properties good electrostrictiveeffects and relaxation of ferroelectric phase transition isshown in Figure 9
Advances in Materials Science and Engineering 7
10
11
12
13
14
046 048 050 052 05416
20
24
28
32
36
40
44
48
52
x = Zr(Zr + Ti)
Pr
(120583C
cm2)
Pr
Ec
Ec
(kV
cm
)
Figure 7 The 119875119903and the 119864
119888as a function of ZrTi ratios
2200
2400
2600
2800
3000
3200
3400
040
045
050
055
060
065
070
45 46 47 48 49 50 51 52 53 54 55100
120
140
160
180
200
220
240
T RMPB
x = Zr(Zr + Ti)
Qm
Qm
kp
kp
minusd31
minusd31
(pC
N)
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
Figure 2 Variations of relative content of the tetragonal andrhombohedra phases with ZrTi ratio
tetragonal and rhombohedra phases and the exact compo-sition of the MPB in chemically homogeneous PZT-PMnN-PSN ceramics were determined
2 Experimentals
The polycrystalline samples of PZT-PMnN-PSN were syn-thesized by columbite precursor method The raw materialsincluding powders (high purity) of PbO (99) ZrO
2(999)
TiO2(99) MnCO
3(99) Sb
2O3(99) and Nb
2O5
(999) for the given composition were weighted by moleratio First the finely mixed powder of MnCO
3and Nb
2O5
Sb2O3and Nb
2O5are mixed in a Teflon-mortar for about
10 h in an acetone medium and then calcined at 1200∘C inan alumina crucible for 3 h The calcined powder was thengrinded andmixed bymortar againwith PbO ZrO
2andTiO
2
for 30 h The finely mixed powder was calcined at 850∘C for2 h
The ground materials were pressed into disk 12mmin diameter and 15mm in thickness under 100MPa Thesamples were sintered in a sealed alumina crucible withPbZrO
3coated powder at temperature 1150∘C for 2 h
Scanning electron micrograph of the sample was taken atroom temperature The sintered pellet was polished andsilver electroded and connected to an LCR meter (HiokiJapan) for dielectric measurement The frequency depen-dence of dielectric constant and loss tangent were obtainedusing the LCR meter in the frequency range from 01 kHzto 500 kHz The polarization-electric field (P-E) hystere-sis loops were measured by a Sawyer-Tower circuit at50Hz
As-sintered samples were ground and polished to removethe surface layer for X-ray diffraction (XRD DMAX-RBRigaku Japan) CuK120572 radiationwith a step of 001 s was usedThe microstructure of the samples was examined by using ascanning electron microscope (SEM)The electromechanicalcoupling factor (119896
119901) mechanical quality factor (119876
119898) and
piezoelectric coefficient (11988931) were calculated by using the
resonance-antiresonance method The dielectric constant
was calculated from the capacitance and the dimension of thesamples
3 Results and Discussion
31 Structure and Microstructure It is reported that tetrag-onal rhombohedra and T-R phases were identified by ananalysis of the peaks (002 (tetragonal) 200 (tetragonal) and200 (rhombohedra)) in the 2120579 range 43∘ndash47∘ The splitting of(002) and (200) peaks indicates that they are the ferroelectrictetragonal phase (FT) while the single (200) peak showsthe ferroelectric rhombohedra phase (FR) [1 6 13] Figure 1shows the XRD patterns of PZT-PMnN-PSNwith ZrTi ratioat 5446 up to 4654 Triplet peaks indicate that the samplesconsist of a mixture of tetragonal and rhombohedra phases
A transition from tetragonal phase to rhombohedra phaseis observed as ZrTi ratio increases The multiple peakseparation method was used to estimate the relative fractionof coexisting phases The relative phase fraction was thencalculated by the following equations [14]
With increasing ZrTi ratio tetragonal relative fractiondecreases and rhombohedra relative fraction increases Theanalysis of the relative phase fraction in the PZT-PMnN-PSNsystem indicates that tetragonal and rhombohedra phasescoexist in the composition range for 048 le 119909 le 052 as shownin Figure 2
Figure 3 shows the SEM image of the fractured surfaceof PZT-PMnN-PSN ceramics at different ZrTi ratios It isobserved from the micrographs that the average grain size ofsamples are increased with the increasing amount of ZrTiratio However when further increasing the ZrTi ratio to5149 the average grain size is reduced These results are ingood agreement with the reported in the literature [15]
32 Dielectric and Ferroelectric Properties
321 The Influence of ZrTi Ratio on the Dielectric PropertiesFigure 4 shows the temperature dependence of dielectricpermittivity and dielectric loss tan 120575 of PZT-PMnN-PSNsystem (1 kHz) with ZrTi ratios 4654 up to 5446 respec-tively As shown in Figure 4 all the samples in morphotropicphase boundary region (ZrTi = 4852minus5248) exhibit typ-ical relaxor ferroelectric behavior around The dielectricresponses are characterized by diffuse dielectric peaks anda slight shift of permittivity of maximum toward highertemperature with increasing frequencies
By comparing the curves in Figure 1 we see that thebroadness of dielectric response increases with an increase inZrTi ratio and the largest is at ZrTi = 4951 The tempera-ture of dielectric permittivity maximum also increases withincrease of ZrTi ratio All samples have a temperature called
4 Advances in Materials Science and Engineering
MZ46 MZ47
MZ48 MZ49
MZ50 MZ51
MZ52 MZ53
Figure 3 Surface morphologies observed by SEM of PZT-PMnN-PSN ceramics at various ratios of ZrTi
Burn temperature at which dielectric response starts comply-ing Curie-Weiss law and the system starts the transition intoparaelectric phase
Figure 5 shows Curie-Weiss dependence of the permit-tivity of the samples at temperatures start to 119879
119861 The fitting
parameters [14] are given in Table 1From Table 1 we can see that all the temperature values
extend to decrease with the increase of ZrTi ratio
322 The Influence of ZrTi Ratio on the Ferroelectric Proper-ties Figure 6 shows 119875-119864 hysteresis loops of all samples Thewell-saturated hysteresis loops were observed and the values
of remanent polarization (119875119903) and coercive field (119864
119888) were
presented in Table 2Itrsquos demonstrated that the hysteresis loops of all samples
are of typical forms characterizing ferroelectric materialsThe remanent polarization (119875
119903) reaches the maximum value
of 492 120583Ccm2 and The coercive field (119864119888) reaches the
minimum value of 1028 kVsdotcmminus1 at ZrTi = 4951 (Figure 7)
4 Piezoelectric Properties
Figure 8 shows the piezoelectric and dielectric propertiesas a function of ZrTi ratio PZT-PMnN-PSN exhibits high
Advances in Materials Science and Engineering 5
100 150 200 250 300 350 400 4500
5000
10000
15000
20000
25000
30000
M046M047
M048
M049M050
M051
M052M053
M054120576
T (∘C)
(a)
50 100 150 200 250 300 350 400 450000
005
010
015
M046
M047
M048
M049M051
M050M052
M053
M054
T (∘C)
tan120575
(b)
Figure 4 (a) Dielectric constant and (b) loss tangent of PZT-PMnN-PSN at various ZrTi ratios
200 250 300 350 400 45000
200 250 300 350 400 45
Experimental dataFitting linear
M046 M047 M048
M049 M050
M052
M051
M053 M054
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
Figure 5 Curie-Weiss dependence of the permittivity of the samples at temperatures start to 119879119861
6 Advances in Materials Science and Engineering
0 10 20 30 40 50 60
0
20
40
60
80
0 10101010100101001010100001010011 20 30 400
0
2000002000202020000020002
M046 M047 M048
M049 M050 M051
M052 M053 M054
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
Figure 6 119875-119864 hysteresis loops of PZT-PMnN-PSN samples
Table 1 Dielectric properties and fitting parameters of PZT-PMnN-PSN ceramics
piezoelectric coefficient and electromechanical coupling fac-tor around the MPB From the trend of the variation ofpiezoelectricity it reaches the maximum values of 119889
Simple diagram phase of PZT-PMnN-PSN ceramicsnear MPB which is attractive system displaying excellentpiezoelectric and dielectric properties good electrostrictiveeffects and relaxation of ferroelectric phase transition isshown in Figure 9
Advances in Materials Science and Engineering 7
10
11
12
13
14
046 048 050 052 05416
20
24
28
32
36
40
44
48
52
x = Zr(Zr + Ti)
Pr
(120583C
cm2)
Pr
Ec
Ec
(kV
cm
)
Figure 7 The 119875119903and the 119864
119888as a function of ZrTi ratios
2200
2400
2600
2800
3000
3200
3400
040
045
050
055
060
065
070
45 46 47 48 49 50 51 52 53 54 55100
120
140
160
180
200
220
240
T RMPB
x = Zr(Zr + Ti)
Qm
Qm
kp
kp
minusd31
minusd31
(pC
N)
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
Figure 3 Surface morphologies observed by SEM of PZT-PMnN-PSN ceramics at various ratios of ZrTi
Burn temperature at which dielectric response starts comply-ing Curie-Weiss law and the system starts the transition intoparaelectric phase
Figure 5 shows Curie-Weiss dependence of the permit-tivity of the samples at temperatures start to 119879
119861 The fitting
parameters [14] are given in Table 1From Table 1 we can see that all the temperature values
extend to decrease with the increase of ZrTi ratio
322 The Influence of ZrTi Ratio on the Ferroelectric Proper-ties Figure 6 shows 119875-119864 hysteresis loops of all samples Thewell-saturated hysteresis loops were observed and the values
of remanent polarization (119875119903) and coercive field (119864
119888) were
presented in Table 2Itrsquos demonstrated that the hysteresis loops of all samples
are of typical forms characterizing ferroelectric materialsThe remanent polarization (119875
119903) reaches the maximum value
of 492 120583Ccm2 and The coercive field (119864119888) reaches the
minimum value of 1028 kVsdotcmminus1 at ZrTi = 4951 (Figure 7)
4 Piezoelectric Properties
Figure 8 shows the piezoelectric and dielectric propertiesas a function of ZrTi ratio PZT-PMnN-PSN exhibits high
Advances in Materials Science and Engineering 5
100 150 200 250 300 350 400 4500
5000
10000
15000
20000
25000
30000
M046M047
M048
M049M050
M051
M052M053
M054120576
T (∘C)
(a)
50 100 150 200 250 300 350 400 450000
005
010
015
M046
M047
M048
M049M051
M050M052
M053
M054
T (∘C)
tan120575
(b)
Figure 4 (a) Dielectric constant and (b) loss tangent of PZT-PMnN-PSN at various ZrTi ratios
200 250 300 350 400 45000
200 250 300 350 400 45
Experimental dataFitting linear
M046 M047 M048
M049 M050
M052
M051
M053 M054
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
200 250 300 350 400 45000
Experimental dataFitting linear
T (∘C)
20 times 10minus4
15 times 10minus4
10 times 10minus4
50 times 10minus5
1120576
998400
Figure 5 Curie-Weiss dependence of the permittivity of the samples at temperatures start to 119879119861
6 Advances in Materials Science and Engineering
0 10 20 30 40 50 60
0
20
40
60
80
0 10101010100101001010100001010011 20 30 400
0
2000002000202020000020002
M046 M047 M048
M049 M050 M051
M052 M053 M054
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
0 10 20 30 40 50 60
0
20
40
60
80
minus20
minus40
minus60
minus80
minus10
minus20
minus30
minus40
minus50
minus60
P(120583
Ccm
2)
E (kVcm)
Figure 6 119875-119864 hysteresis loops of PZT-PMnN-PSN samples
Table 1 Dielectric properties and fitting parameters of PZT-PMnN-PSN ceramics
piezoelectric coefficient and electromechanical coupling fac-tor around the MPB From the trend of the variation ofpiezoelectricity it reaches the maximum values of 119889
Simple diagram phase of PZT-PMnN-PSN ceramicsnear MPB which is attractive system displaying excellentpiezoelectric and dielectric properties good electrostrictiveeffects and relaxation of ferroelectric phase transition isshown in Figure 9
Advances in Materials Science and Engineering 7
10
11
12
13
14
046 048 050 052 05416
20
24
28
32
36
40
44
48
52
x = Zr(Zr + Ti)
Pr
(120583C
cm2)
Pr
Ec
Ec
(kV
cm
)
Figure 7 The 119875119903and the 119864
119888as a function of ZrTi ratios
2200
2400
2600
2800
3000
3200
3400
040
045
050
055
060
065
070
45 46 47 48 49 50 51 52 53 54 55100
120
140
160
180
200
220
240
T RMPB
x = Zr(Zr + Ti)
Qm
Qm
kp
kp
minusd31
minusd31
(pC
N)
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
piezoelectric coefficient and electromechanical coupling fac-tor around the MPB From the trend of the variation ofpiezoelectricity it reaches the maximum values of 119889
Simple diagram phase of PZT-PMnN-PSN ceramicsnear MPB which is attractive system displaying excellentpiezoelectric and dielectric properties good electrostrictiveeffects and relaxation of ferroelectric phase transition isshown in Figure 9
Advances in Materials Science and Engineering 7
10
11
12
13
14
046 048 050 052 05416
20
24
28
32
36
40
44
48
52
x = Zr(Zr + Ti)
Pr
(120583C
cm2)
Pr
Ec
Ec
(kV
cm
)
Figure 7 The 119875119903and the 119864
119888as a function of ZrTi ratios
2200
2400
2600
2800
3000
3200
3400
040
045
050
055
060
065
070
45 46 47 48 49 50 51 52 53 54 55100
120
140
160
180
200
220
240
T RMPB
x = Zr(Zr + Ti)
Qm
Qm
kp
kp
minusd31
minusd31
(pC
N)
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
piezoelectric coefficient and electromechanical coupling fac-tor around the MPB From the trend of the variation ofpiezoelectricity it reaches the maximum values of 119889
Simple diagram phase of PZT-PMnN-PSN ceramicsnear MPB which is attractive system displaying excellentpiezoelectric and dielectric properties good electrostrictiveeffects and relaxation of ferroelectric phase transition isshown in Figure 9
Advances in Materials Science and Engineering 7
10
11
12
13
14
046 048 050 052 05416
20
24
28
32
36
40
44
48
52
x = Zr(Zr + Ti)
Pr
(120583C
cm2)
Pr
Ec
Ec
(kV
cm
)
Figure 7 The 119875119903and the 119864
119888as a function of ZrTi ratios
2200
2400
2600
2800
3000
3200
3400
040
045
050
055
060
065
070
45 46 47 48 49 50 51 52 53 54 55100
120
140
160
180
200
220
240
T RMPB
x = Zr(Zr + Ti)
Qm
Qm
kp
kp
minusd31
minusd31
(pC
N)
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
Figure 8 Piezoelectric properties of PZT-PMnN-PSN at variousZrTi ratios
0
50
100
150
200
250
300
350
400
450
500
46 48 50 52 54
Ferroelectric rhombohedral
Ferroelectric relaxor
Paraelectric
Ferroelectric tetragonal Ferroelectric
x = Zr(Zr + Ti)
TBTCTm
Tem
pera
ture
(∘C)
tetragonal + rhombohedral
Figure 9 Simple diagram phase of PZT-PMnN-PSN system nearMPB
5 Conclusion
The results obtained from the experiment are as follows
(1) PZT-PMnN-PSN ceramics with 7 wt excess PbOwere prepared by columbite method
(2) The structure of ceramics sintered at 1150∘C shows thepure perovskite structure in all ceramics specimensthe structure of PZT-PMnN-PSN ceramics was trans-formed from tetragonal to rhombohedra with ZrTiratio increased in system
(3) The composition of PZT-PMnN-PSN ceramics nearthe morphotropic phase boundary obtained is theratio of ZrTi = 4951 At this ratio the ceramichas the optimal electromechanical properties the119896119901= 061 the 120576max = 29520 the 11988931 = minus236
pCN the 119876119898= 2400 high remanent polarization
(119875119903= 492 120583Csdotcmminus2) and low coercive field 119864
119888=
1028 kVsdotcmminus1(4) The piezoelectric ceramic with ZrTi ratio of 4951
may be suitable for piezoelectric transformer applica-tions and other high power devices
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgment
This work is supported by the National Foundation for Sci-ence and Technology Development (NAFOSTED) no103020609
References
[1] F Gao L Cheng RHong J Liu CWang andC Tian ldquoCrystalstructure and piezoelectric properties of xPb(Mn
13Nb23)O3ndash
(02-x)Pb(Zn13Nb23)O3ndash08Pb(Zr
052Ti048
)O3
ceramicsrdquoCeramics International vol 35 no 5 pp 1719ndash1723 2009
[2] Z Necira A Boutarfaia M Abba H Menasra and NAbdessalem ldquoEffects of thermal conditions in the phase for-mation of undoped and doped Pb(Zr
1minusxTix)O3 solid solutionsrdquoMaterials Sciences and Applications vol 4 no 5 pp 319ndash3232013
[3] Y Xu Ferroelctric Materials and Their Applications North-Holland London UK 1991
[4] J Yoo Y Lee K Yoon et al ldquoMicrostructural electricalproperties and temperature stability of resonant frequencyin Pb(Ni
12W12)O3ndashPb(Mn
13Nb23)O3ndashPb(ZrTi)O
3ceramics
for high-power piezoelectric transformerrdquo Japanese Journal ofApplied Physics A vol 40 no 5 pp 3256ndash3259 2001
[5] R Muanghlua S Niemchareon W C Vittayakorn and NVittayakorn ldquoEffects of ZrTi ratio on the structure andferroelectric properties in PZTndashPZNndashPMN ceramics near themorphotropic phase boundaryrdquo Advanced Materials Researchvol 55-57 pp 125ndash128 2008
[6] F Kahoul L Hamzioui N Abdessalem and A Boutar-faia ldquoSynthesis and piezoelectric properties of Pb
098Sm002
8 Advances in Materials Science and Engineering
[(ZryTi1minusy)098(Fe3+
12Nb5+12)002
]O3
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
ceramicsrdquo Materials Sci-ences and Applications vol 3 pp 50ndash58 2012
[7] N D T Luan L D Vuong and B C Chanh ldquoMicrostructureferroelectric and piezoelectric properties of PZTndashPMnSbNceramicsrdquo International Journal ofMaterials and Chemistry vol3 pp 51ndash58 2013
[8] M Kobune Y Tomoyoshi A Mineshige and S Fujii ldquoEffectsof MnO
2addition on piezoelectric and ferroelectric properties
of PbNi13Nb23O3ndashPbTiO
3ndashPbZrO
3ceramicsrdquo Journal of the
Ceramic Society of Japan vol 108 no 7 pp 633ndash637 2000[9] S J Yoon A Joshi and K Uchino ldquoEffect of additives on the
electromechanical properties of Pb(ZrTi)O3ndashPb(Y
23W13)O3
ceramicsrdquo Journal of the American Ceramic Society vol 80 no4 pp 1035ndash1039 1997
[10] Y K Gao Y H Chen J H Ryu K J Uchino and DViehland ldquoEu and Yb substituent effects on the propertiesof Pb(ZrM
052Ti048
)O3ndashPb(Mn
13Sb23)O3ceramics develop-
ment of a new high-power piezoelectric with enhanced vibra-tional velocityrdquo Japanese Journal of Applied Physics vol 40 no2 pp 687ndash693 2001
[11] Z L Gui L T Li H Q Lin and X W Zhang ldquoLow tem-perature sintering of lead magnesium nickel niobate zirconatetitanate (PMNndashPNNndashPZT) piezoelectric ceramic with highperformancesrdquo Ferroelectrics vol 101 no 1 pp 93ndash99 1990
[12] Z Yang H Li X Zong and Y Chang ldquoStructure and electricalproperties of PZTndashPMSndashPZN piezoelectric ceramicsrdquo Journalof the European Ceramic Society vol 26 no 15 pp 3197ndash32022006
[13] H Fan and H Kim ldquoPerovskite stabilization and electrome-chanical properties of polycrystalline lead zinc niobate-leadzirconate titanaterdquo Journal of Applied Physics vol 91 no 1 pp317ndash322 2002
[14] A Quintana-Nedelcos A Fundora H Amorın and J MSiqueiros ldquoEffects of Mg addition on phase transition anddielectric properties of Ba(Zr
005Ti095
)O3systemrdquo The Open
Condensed Matter Physics Journal vol 2 pp 1ndash8 2009[15] L D Vuong P D Gio T Van Chuong D T H Trang D
V Hung and N T Duong ldquoEffect of ZrTi ratio content onsome physical properties of the low temperature sintering PZTndashPZNndashPMnN ceramicsrdquo International Journal of Materials andChemistry vol 3 no 2 pp 39ndash43 2013
