Research Article Dielectric Properties of PbNb 2 O 6 up to...

Hindawi Publishing CorporationJournal of MaterialsVolume 2013 Article ID 702946 15 pageshttpdxdoiorg1011552013702946

Research ArticleDielectric Properties of PbNb

2O6

up to 700∘C fromImpedance Spectroscopy

Kriti Ranjan Sahu1 and Udayan De2

1 Physics Department Egra SSB College Egra Purba Medinipur West Bengal 721429 India2 Kendriya Vihar C-460 VIP Road Kolkata 700052 India

Correspondence should be addressed to Udayan De ude2006gmailcom

Received 28 January 2013 Revised 28 March 2013 Accepted 29 March 2013

Academic Editor Iwan Kityk

Copyright copy 2013 K R Sahu and U DeThis is an open access article distributed under theCreativeCommonsAttribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Piezoelectric materials have wide band gap and no inversion symmetry Only the orthorhombic phase of lead metaniobate(PbNb

2O6) can be ferroelectric and piezoelectric below Curie temperature but not the rhombohedral phase High temperature

piezoelectric applications in current decades have revived international interest in orthorhombic PbNb2O6 synthesis of which

in pure form is difficult and not well documented Second problem is that its impedance spectroscopy (IS) data analysis is stillincomplete Present work attempts to fill up these two gaps Presently found synthesis parameters yield purely orthorhombicPbNb

2O6 as checked by X-ray Rietveld analysis and TEM Present 20Hz to 55MHz IS from room temperature to 700∘C shows

its ferroelectric Curie temperature to be one of the highest reported gt574∘C for 05 kHz and gt580∘C for 55MHz Dielectriccharacteristics and electrical properties (like capacitance resistance and relaxation time of the equivalent CR circuit AC and DCconductivities and related activation energies) as derived here from a complete analysis of the IS data are more extensive thanwhat has yet been reported in the literature All the properties show sharp changes across the Curie temperature The temperaturedependence of activation energies corresponding to AC and DC conductivities has been reexamined

1 Introduction

A generator of pressure or movement or ultrasonic waveand their sensordetector can be fabricated utilizing inverseand direct piezoelectric effect respectivelyThese possibilitiesopened up a huge array [1] of medical industrial andother applications of piezoelectric materials with significantcommercial implications Commercial piezoelectric materi-als have mostly been barium titanate (BT) lead zirconatetitanate (PZT) or materials based on BT or PZT But Curietemperature (119879

119888) the upper limit for piezoelectricity is at best

130∘C [2] for BT and 365∘C for a modified PZT So higher119879119888materials are being developed worldwide for high tem-

perature (HT) applications Lead metaniobate (PbNb2O6)

shortened here as PNO with a higher Curie temperature(517 to 570∘C in different papers) is one of the presentcandidate materials [2ndash14] It was discovered [3] in 1953However synthesis of its piezoelectric phase the metastableorthorhombic structure in a pure state is difficult [4] Duringthe preparation of the orthorhombic PNO by quenching

from a temperature above 1250∘C a few competing com-pounds and phases (like the rhombohedral PNO phase) tendto form The rhombohedral PNO is not piezoelectric Infact the difficulty [4] of forming single-phase and high-density orthorhombic PNO together with the success of BTPZT and related piezomaterials for near room temperatureapplications somewhat halted R amp D on PNO after theinitial years of pioneering work and publications [5ndash9] Inthe meantime a need has developed for high temperature(HT) piezoelectric materials (i) for HT ultrasonic imaging ofnuclear fuel rods through molten metal coolants [15] in FastBreeder Reactors and (ii) for HT applications like sensors incar exhaust systems So since the late nineties work on PNOhas been revived by a few groups (Table 1) in search of higherCurie temperature materials The stable forms of PbNb

2O6

are rhombohedral (at low temperature) and tetragonal (athigh temperature) Quenching from the tetragonal form asmentioned earlier leads to metastable orthorhombic format room temperature Roth showed by X-ray diffraction

2 Journal of Materials

[5 6] that the orthorhombic PNO (ferroelectric) changes to atetragonal structure (paraelectric) above sim570∘C

Goodman [3] had earlier concluded the 119879(Curie) of

quenched PNO to be 570∘C from their dilatometric anddielectric characterizations Although this temperature isregarded even in recent papers [10] as the Curie temperatureof PbNb

2O6 almost all the recent electrical measurements

have obtained much lower values of its Curie temperature(Table 1) Reference [10] quoted 119879

(Curie) of 500∘C for Ferro-

perm (Denmark) PNO samples (1995) and 495∘C forMorganMatroc (UK) PNO samples (1997) Lower 119879

(Curie) in thesecommercial samples may or may not be due to efforts tooptimize other piezoelectric parameters Table 1 has beencompiled from recent publications It shows 119879

(Curie) to be inthe range 517∘C to 540∘C only except in present samplesSo there is a need to optimize preparation conditions ofquenched PbNb

2O6to get highest possible Curie tempera-

ture high purity and high density A pointer in this directionis our observation on quenched PNO [11] of an endothermicsignal at 5706∘C in Differential Scanning Calorimetry [12]

Here our preparation of high quality orthorhombic PNOand results of our impedance spectroscopy up to 700∘C andover a wide frequency range from 20Hz to 55MHz witha detailed analysis have been presented Intrinsic cationicdefects in niobates like LiNbO

3and their role are well known

[16] Likely lattice defects in a quench-prepared PbNb2O6

sample should similarly be regarded as an intrinsic part ofthe sample The structure of the samples has therefore beencharacterized fully before other studies Although some workon PNO (Table 1) and a few on various targeted chemicalsubstitutions in PNOhave been reported in the literature notall possible dielectric and electrical parameters for PNO itselfhave yet been derived from IS data This has been attemptedhere The dielectric response in such an electroceramic isknown to be complex with many contributions that need tobe known and understood So desirable observations likethe highest 119879

(Curie) as well as all uncommon observations ofthe present work are reproduced All possible data analysishas been carried out yielding important parameters like bulkresistance relaxation times activation energies AC and DCconductivity and phase angle

2 Materials and Methods

Aldrich lead(II) oxide (PbO 99999 yellowish orange andMelting Point = 886∘C) and niobium pentoxide (999 GR)of Loba Chemie weighed in proper proportion to givePb Nb = 1 2 plus 2 of excess PbO have been well groundunder isopropyl alcohol dried and pelletized Additions ofexcess PbO were introduced by some earlier workers tocompensate possible evaporative loss of PbO To get bestPbNb

2O6 present firings have been done in stages at 1050∘C

1290∘C and 1270∘C in a box furnace with PID temperaturecontroller Extra PbO (3) has been added before the 3rdfiring All our firings have been done in palletized form toprovide intimate contact and reduce Pb loss But grindingand repalletizing at each step have also been undertakento improve mixing and the sample quality After the last

Table 1 Comparison of recently reported Curie temperatures oforthorhombic PbNb2O6 samples

Sample SinteringCurie temperature 119879

(Curie) in∘CTemp

(∘C)Time(h)

Present 1270 45 119879(Curie) gt 576 for 40MHz and

gt574 for 05 kHz[17] 1270 45 517[18] 1270 mdash 534 and 540 (both at 10 kHz)[19] mdash mdash 540 (presumably at 80 kHz)[20] 1240ndash1260 4 530 (at 10 kHz)

[13] 1270 45 531 (at 1 kHz) 528 (at 1MHz) and533 (at 10MHz)

firing the samples have been quenched The samples havebeen characterized by XRD with Rietveld analysis [11] andTransmission Electron Microscopy (TEM)

The impedance spectroscopy has been carried out usingSolatron ldquoSI 1260 Impedance Gain Phase Analyzerrdquo with ahigh temperature attachment Our PNO pellets (diametersim12mm and 22 to 24mm thick) have not been poled beforemeasurement Silver paint coat on the flat faces of the pelletunder study served as the electrodes for IS measurementsThis measurement of 120576

1015840 and 120576

10158401015840 (the real and imaginarycomponents respectively of the relative dielectric constantie permittivity) has been done for different measuringfrequencies at different values the sample temperature (119879)while heating from room temperature to 700∘C

3 Results and Discussion

XRD pattern and Rietveld analysis [11] Figure 1(a) con-firmed the orthorhombic structure and absence of any otherphase The smallness of the difference of the fitted graphand raw data proved our Rietveld fit to be good It yields119886 = 176468(7) A 119887 = 179512(7) A and 119888 = 38704(1) AThe samples showed about 80 of the theoretical densityon average TEM diffractograms [6] with the electron beamon individual grains of the ceramic sample always gavediffraction patterns that matched these lattice parametersfrom XRD result One TEM diffraction pattern is shown inFigure 1(b) This way all of the nearly forty grains examinedhave been found to be in orthorhombic phase

Figures 2ndash4 show 120576

1015840 versus frequency 120576

10158401015840 versus fre-quency and tan 120575 = 120576

10158401015840120576

1015840 versus frequency results (over20Hz to 55MHz range) for 12 temperatures from 50∘Cto 700∘C In Figure 2 real part (1205761015840) of dielectric constantdecreases with increase of measuring frequency up to aboutln119891 = 12 to 14 region implying sim162 kHz to sim1203 kHzregion and then increases sharply with increase of fre-quency as reported earlier [13] for all temperatures exceptat low temperatures like 200∘C Moreover 1205761015840 is low and lessdependent on frequency at low temperatures up to 300∘Cleading to overlap of several graphs It increases with increaseof temperature up to 573∘C Graph of 120576

1015840 shows signifi-cantly increased values in the 573∘C graphs with respect to

Journal of Materials 3

10 20 30 40 50 60 70 80minus2000

minus1000

0

1000

2000

3000

4000

5000

6000

X-ra

y in

tens

ity (a

u)

Scattering angle 2120579 (∘)

Orthorhombic PbNb2O6

(a) (b)

Figure 1 (a) Rietveld fit (red graph) to XRD data points (black circles) for orthorhombic PbNb2O6with their difference shown by the

continuous curve in the smaller-sized graph The vertical blue bars below the main graph are the calculated peak positions (b) Electrondiffraction pattern for HR Transmission Electron Microscopy on a selected grain (microcrystal) of quenched lead metaniobate (PNO)

3 4 5 6 7 8 9 10 11 12 13 14 15 16

0

2000

4000

6000

8000

10000

12000

6 8 10 12 14 160120576998400

1

2

3

4times103

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)

Figure 2 Frequency dependence of the real part of dielectricconstant (1205761015840) in the frequency range 20Hz (ln119891 = 2995) to 55MHz(ln119891 = 1552) compiled fromheating runs at different temperaturesfor quenched PNO sample the orthorhombic phase of PbNb

2O6

The inset is an enlarged view of the variation of 120576

1015840 in the higherfrequency range

the 570∘C graph This temperature is the region of ferroelec-tric to paraelectric phase transition as is clearer in graph ontemperature variation (Figure 5) One must note the interest-ing decrease of 1205761015840 with further increase of temperature above573∘CThis in fact shows up in 120576

1015840 versus 119879 plot as peaking ataround 573∘C Here it was studied up to 700∘CThe values atdifferent temperatures of dielectric dispersion with respect to

frequency which will be proportional to d1205761015840d(ln119891) will bediscussed from the low frequency specifically ln119891 (Hz) lt 7part of Figure 2 At a low temperature of 100∘C d1205761015840d(ln119891) =

2483 plusmn 0739 only increasing to 41158 plusmn 7805 at 300∘Cwhereas at the high temperature of 573∘C d1205761015840d(ln119891) =

minus4121578 plusmn 226784 a high valueIn Figure 3 frequency dependence of 12057610158401015840 or the imaginary

part of relative permittivity is more at low frequencies andhigher temperatures the 12057610158401015840 versus frequency graph for 700∘Cbeing at top in the lower frequency region Here 12057610158401015840 decreasessteeply as frequency increases from 20Hz to about ln119891 = 8

implying 119891 = 298 kHz A weak peaking of 120576

10158401015840 at ln119891 =

138 implying 119891 = 9846 kHz is visible for graphs forlow temperatures like 50∘C 300∘C 500∘C and 550∘C in theenlarged view Our higher temperature graphs show no peakin this temperature region but only a slow increase of 12057610158401015840 toallow peaking at higher frequencies This fall and peakingof 120576

10158401015840 has been shown and discussed by earlier workers[13] although the details differ Dielectric loss (tan 120575) inFigure 4 approximately follows 12057610158401015840 with respect to frequencyand temperature dependence

Figures 5 and 6 are plots with respect to temperature of 1205761015840and tan 120575 = 120576

10158401015840120576

1015840 respectivelyThepeak value of 1205761015840 is denotedby 120576

1015840

max and its position on the temperature axis by 119879119898 Data

for eight frequencies selected out of 20Hz to 55MHz datain Figures 2ndash4 have been plotted in Figures 5 and 6 to avoidoverlaps and provide a clearer view of the graphs

Fall of 1205761015840 and hence of the dielectric susceptibility 1205941015840=(1205761015840 minus 1) with increasing 119879 a characteristic of the paraelectricphase and exhibited here for 119879 gt 119879

119898region is due to

opposition of the increasing thermal agitation to dipolealignment The rise of 120576

1015840 with 119879 in the 119879 lt 119879119898region is

believed to be achieved by the increase in the number ofdipoles available for alignment [21] Sharpness of the peakat 119879119898indicates near absence of diffused scattering in present

samples as discussed elaborately later Let aminor peculiarity


3 4 5 6 7 8 9 10 11 12 13 14 15

0

10 11 12 13 14 15 16

0

times102times105

2

4

6

8

10

12 5

4

3

2

1

120576998400998400

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)

Figure 3 Frequency dependence of the imaginary part (12057610158401015840) of dielectric constant in the frequency range 20Hz to 55MHz compiled fromheating runs at different temperatures for quenched PNO sample the orthorhombic phase of PbNb

2O6 The inset is an enlarged view of the

variation of 12057610158401015840 in the higher frequency range

4 6 8 10 12 14 16

0

20

40

60

80

100

120

10 11 12 13 14 150

02

04

06

08

1

Die

lect

ric lo

ss (t

an120575

)

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)

Figure 4 Frequency dependence of the dielectric loss (tan 120575) in the frequency range 20Hz to 55MHz compiled fromheating runs at differenttemperatures for quenched PNO sample the orthorhombic phase of PbNb

2O6

be discussed first A wide minimum (Figure 5) appearingat 300∘C for frequencies 05 kHz 1 kHz and 5 kHz in 120576

1015840

versus 119879 as well as in tan 120575 versus 119879 graph (Figure 6) cannotbe readily explained However the more important featureof this work is the large permittivity peak at 119879

119898with 119879

119898

ranging from 574∘C to 576∘C as the measurement frequencyis increased from 05 kHz to 4MHz as mentioned earlierIn Figure 7 the peak value 1205761015840max of 120576

1015840 shows a sharp fallinitially and then a slow rise with increase of measuring

frequency The value of 1205761015840max decreases from 11623 to 1450 asthe frequency (119891) increases from 20Hz to 1MHz Then for119891 gt 1MHz the value of 1205761015840max increases slowly being about5465 at 55MHz The prominent peak of the imaginary part120576

10158401015840 in the 120576

10158401015840 versus 119879 graph can be seen to be around 119879119898as

expected The dielectric loss (tan 120575) also peaks at around 119879119898

Above119879119898 1205761015840 decreases with increase of119879 and hence the

material is obviously paraelectric above 119879119898 It is ferroelectric

below 119879119898 This transition temperature gives [22] the Curie


100 200 300 400 500 600 7000

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

250 300 3500

100

200

300 560 580 600 620 640

1000

2000

3000

4000

PNQ

4 MHz3 MHz50 kHz30 kHz

10 kHz5 kHz1 kHz05 kHz

Temperature (∘C)

120576998400

Figure 5 Temperature dependence of the real part (1205761015840) of dielectric constant in the temperature range of 50∘C to 700∘C at differentfrequencies for quenched PNO sample the orthorhombic phase of PbNb

2O6

100 200 300 400 500 600 70005

10152025303540455055

260 325minus036minus018

0018036054072

09108

500 550 6000

044088132176

22264308352396

500 kHz

4 MHz3 MHz

50 kHz


Temperature (∘C)

tan120575

Figure 6 Temperature dependence of the dielectric loss (tan 120575) in the range 50∘C to 700∘C at different frequencies for quenched PNO samplethe orthorhombic phase of PbNb

2O6 Two insets magnify two important features

temperature So present impedance spectroscopy measure-ments indicate a high Curie temperature that depends onfrequency 576∘C for 40MHz and 580∘C for 55MHz forexample

The plot of 11988510158401015840 (imaginary part of the impedance) versus119885

1015840 (real part of the impedance) called Nyquist diagram [23]is based on the well-known Cole-Cole plot of 12057610158401015840 versus 120576

1015840The 119885

10158401015840 versus 119885

1015840 plot for our orthorhombic PNO is shownin Figures 8(a) and 8(b) The straight line segments joiningof the data points in Figures 8(a) and 8(b) are drawn only as

a guide to the eye Single semicircular nature of the plots isclearer in the higher temperature plots as the lower tempera-ture plots like that for 200∘C in the insert of Figure 8(a) showa near linear rise possible for a large semicircle An importantobservation is that the Nyquist diagram here shows only onesemicircular arc [23] over the studied frequency range 20Hzto 55MHz One semicircle implies only one contributionhere from the sample grains and not from any second source(eg grain boundaries or electrode effect) A sample with onesemicircle Nyquist diagram or Cole-Cole plot is equivalent


0 11 M 22 M 33 M 44 M 55 MFrequency (Hz)

times103

12

10

8

6

4

0

2

120576998400m

ax

Figure 7 The maximum value (1205761015840max) of the real part of dielectric constant in the in the temperature range of 50∘C to 700∘C as a function offrequency (Hz) for quenched PNO sample the orthorhombic phase of PbNb

2O6

0 200 k 400 k 600 k 800 k

0

200 k

400 k

600 k

800 k

010

M20

M30

M40

M

020 M40 M60 M80 M

100 M120 M

120596

Temperature (∘C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

500∘C550∘C570∘C573∘C

600∘C

200∘C

650∘C700∘C

(a)

0 1 M 2 M 3 M 4 M 5 M 6 M 7 M

0

1 M

2 M

3 M

4 M

5 M

6 M

7 M

Temperature ( C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

120596

400∘C440∘C460∘C480∘C

(b)

Figure 8 (a) Plot of the imaginary part 119885imaginary in ohm of impedance versus its real part 119885real in ohm for quenched PNO samplePbNb

2O6in orthorhombic phase at temperatures 500∘C 550∘C 570∘C 573∘C 600∘C 650∘C and 700∘C Since the complex impedance

119885

lowast= 119885real minus 119895119885imaginary quantity (minus119885imaginary) has actually been plotted in the figure (b) Plot of the imaginary part 119885imaginary in ohm of

impedance versus its real part119885real in ohm for the quenched PNO sample PbNb2O6in orthorhombic phase at temperatures 400∘C 440∘C

460∘C and 480∘C Since the complex impedance 119885

lowast= 119885real minus 119895119885imaginary quantity (minus119885imaginary) has actually been plotted in the figure

[23] to a bulk resistance 119877 and a capacitance 119862 in parallelThese elements give rise to a time constant 120591 = 119862119877 thedielectric relaxation time of the basic materialThe frequency120596119898of the peak of the Nyquist diagram can find the relaxation

time 120591 as (120596119898)(120591) = 1 for this peak point [23] At this point

119885

10158401015840 has its maximum value So many authors [24 25] use thefrequency of peak (ie maximum) of 11988510158401015840 versus frequencyplot to find the relaxation time 120591

Present work additionally suggests an alternative method(based [23] on 119885

10158401015840= 1198772 = 119885

1015840 criterion) of determiningrelaxation time (120591) We later compare the two methods withthe finding that they match (Figure 14) fairly well matchbeing better at higher temperatures Often the centre of thesemicircular arc of the Nyquist diagram is not on the1198851015840-axisso that the semicircle is seen to be depressed by an angle (120579)below the 119885

1015840-axis This is the case if there is a distribution


400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600

800Resistance Capacitance

Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C

Figure 9 Bulk resistance 119877 in MΩ and capacitance 119862 in nF ofthe equivalent 119877119862 circuit of quenched PbNb

2O6sample plotted

against temperature 119879 Here 119877 and 119862 have been calculated fromNyquist diagram of 119885

1015840 and 119885

10158401015840 in 20Hz to 55MHz range andthe corresponding time constant 120591 = 119862119877 related to the dielectricrelaxation time

of relaxation times This 120579 is determined by the width of thedistribution of relaxation time

If the semicircle starts near the origin at 1198851015840 = 119877infin

andintercepts the 119885

1015840-axis again at 1198770 119877 = (119877

0minus 119877infin) gives [23]

the bulk resistance Fitting the impedance spectroscopy (11988510158401015840versus 119885

1015840) data usually forming an arch to the equation ofa circle its radius 119903 and 120579 and hence 119877

0can be determined

Bulk resistance 119877 = (1198770minus 119877infin) = 2119903 sdot cos 120579 has thus been

calculated from our data in Figure 8 and plotted in Figure 9It is found that the semicircle of data points for a particulartemperature in Figures 8(a) and 8(b) reduces in size withincrease of temperature implying smaller bulk resistanceof the sample at higher temperatures as documented inFigure 9 Real part 120576

1015840 of permittivity in present samples inthe paraelectric region has been fitted to the modified Curie-Weiss law [26] (11205761015840 minus 1120576

1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is

Curie-Weiss constant and 120574 is the diffusivity parameter with1 lt 120574 lt 2 For a ferroelectric relaxor 120574 is at its highest valueof 2

The previous equation reduces to Curie-Weiss law for 120574 =

1 The full equation can be rewritten as ln(11205761015840 minus 1120576

1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862

119908 So plotting of ln(11205761015840 minus 1120576

1015840

max) versusln(119879minus119879

119898) for different frequencies as shown in Figures 10(a)

and 10(b) gives the fit parameters (Table 2) Present findingthat 120574 is nearly 1 in all cases proves that the relaxor property isminimum for these samples This 120574 = 1 leads to the observedsharpness of the peak at 119879

119898 Relaxor piezoelectric materials

on the other hand show a broadened peakNext AC conductivity (120590ac) has been calculated from

the dielectric loss (tan 120575) data using the empirical formula120590ac = 120596120576

0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10

minus12 Fsdotmminus1 = vacuum permittivity and 119888 = speed of light invacuum Figure 11 presents this result on AC conductivity asa function of 1000119879 Now the maxima in different graphsof Figure 11 (prominent only in high frequency graphs) are at1000119879 sim 118Kminus1 that is at 119879 sim 573

∘C that corresponds

Table 2 Result of fitting 120576 versus119879 data to themodified Curie-Weissequation as detailed in the text

Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840

max55M 5795 plusmn 4 2187 1141 5472630M 5752 plusmn 2 1739 1136 1876120M 5748 plusmn 1 1471 1110 1574250 k 5749 plusmn 1 1236 1035 1752210 k 5738 plusmn 1 5237 1283 3613905 k 5730 plusmn 1 2635 1117 3632501 k 5725 plusmn 1 0877 0744 71035

to the ferroelectric-to-paraelectric transition AC activationenergy (119864ac) was calculated using the empirical Arrheniusrelation 120590ac = 120590

0exp (minus119864ac119896119879)

The aforementioned maximum known to occur inthe AC conductivity graph at around the ferroelectric-paraelectric phase transition temperature (119879

119888) is due to

domain reorientation domain wall motion and the dipolarbehavior [27] In our data in Figure 11 there are three distincttemperature regions of Arrhenius type conduction (a) sim50to sim300∘C section corresponding to [28] electron or holehopping (b)sim400 tosim550∘Cpart due to conduction by smallpolarons and oxygen vacancies and (c) sim580 to sim700∘C hightemperature region due to intrinsic ionic conduction [29]Data in these three regions have been separately fitted to theArrhenius relation as shown in Figure 12The slope of ln(120590ac)versus 1119879 plot gives AC activation energy 119864ac

The previous fitting avoided the region between 300 and400∘C as it showed an unexplained peak However the risein some graphs at sim300∘C to sim322∘C region of Figure 11reminds one of the anomaly at sim300∘C in 120576

10158401015840 versus 119879 aswell as in tan 120575 versus 119879 graphs in Figures 5 and 6 It isnoteworthy that temperature dependence of 120590ac is radicallydifferent below and above this temperature zone indicatingdifferentAC activation energies forAC conductionHoweversomewhat wavy nature of the data at low frequencies and lowtemperatures in this and other work [30] and suggestion ofthe rise by only one point in high frequency graphs preventdefinite conclusions on the riseThese data at low frequencies(here 05 1 and 10 kHz in Figure 11) and low temperature(119879 lt 401

∘C) have not been considered for present ACactivation energy calculation in next paragraph In the hightemperature graph in Figure 12119864ac falls rapidly with increaseof measuring frequency up to 500 kHz and then becomesweakly dependent on frequency at higher frequencies Thelow temperature graph of 119864ac is practically independent offrequency over the range (500 kHz to 5MHz) studied hereAs seen in the graphs the AC activation energy is higher atlower frequencies 05 kHz data giving 0954 eV (with 120590

0=

5756Ωsdotmminus1) for 400 to 550∘C and 117 eV (with 1205900= 1508times

10

3Ωsdotmminus1) for 580 to 700∘C These values fall to 0523 eV

(with 1205900

= 2462Ωsdotmminus1) for 400 to 550∘C and minus1994 eV(with 120590

0= 6253 times 10

minus13Ωsdotmminus1) for 580 to 700∘C that is in

paraelectric region respectively Figure 13 gives the variationof 119885real = 119885

1015840 and 119885imaginary = 119885

10158401015840 against the measuringfrequency Here 119885

1015840 and 119885

10158401015840 graphs are seen to merge in


15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)

Figure 10 (a) Plot of ln(11205761015840minus11205761015840max) versus ln(119879minus119879119898) for quenchedPNOsample the orthorhombic phase of PbNb

2O6 at various frequencies

(3MHz 2MHz 1MHz 50 kHz and 1 kHz) It examines the relationship expected for the paraelectric phase of a normal ferroelectric (b)A specific example of finding the parameters (120574 = 10346 and 119862 = 12356904

∘C) of the modified Curie-Weiss law from the 50 kHz plot ofln(11205761015840 minus 1120576

1015840

max) versus ln(119879 minus 119879119898) for the paraelectric phase of quenched PbNb

2O6 which is orthorhombic

1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0

5 MHz4 MHz3 MHz500 kHz

10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C

Figure 11 Frequency dependence of AC conductivity in the temperature range 50∘C to 700∘C at different frequencies for quenched PNOsample the orthorhombic phase of PbNb

2O6

the high frequency region approaching zero valueThe singlesemicircular Cole-Cole plot suggests an equivalent circuit[23] of resistance 119877 and capacitance 119862 in parallel giving thewell-known complex impedance 119885

lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885

10158401015840 Applying the relation 120591 = 119862119877 and the earlier-mentioned

condition 120596119898120591 = 1 one gets 119885

10158401015840= 1198772 and 119885

1015840= 1198772 So

relaxation time related frequency is the frequency at which119885

1015840 versus frequency and 119885

10158401015840 versus frequency graphs crosseach other making 119885

1015840= 119885

10158401015840 We calculate this relaxationtime and present it as the relaxation time 120591cross in Figure 14


0 1 2 3 4 5minus21minus18minus15minus12minus09minus06minus03

00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C

Figure 12 AC conductivity activation energy 119864119886 as calculated from the slope of the Arrhenius plot of ln(120590ac) versus 1119879 resulting in three

119864119886values for three temperature ranges This figure depicts the variation of 119864

119886with measuring frequency

We determine relaxation time also from the frequency atthe 119885

10158401015840 peak of 119885

10158401015840 versus frequency graphs (Figure 13) asdone by others [30] calling it 120591peak to compare it in Figure 14with 120591cross Figure 14 shows that 120591cross and 120591peak behavesimilarly proving correctness of each approach But these twographs show different values with more relative scatter in the120591peak graph This point shows up again in DC conductivitydiscussion in next paragraphs

The decrease of relaxation time with temperature hasbeen adequately discussed in the literature [31] Relaxationtime for this material is seen to fall with increasing temper-ature except for a prominent peaking at the ferroelectric toparaelectric transition temperature 119877 = (119877

0minus 119877infin) sim 119877

0

since 119877infin

≪ 1198770 This 119877 has already been calculated from

Figure 8 So presently determined 119862119877 = 120591 value gives us 119862These two equivalent circuit parameters 119862 and 119877 have beenpresented in Figure 9 Here there is an impressive peakingof capacitance 119862 at the Curie temperature Another relatedparameter the angle (120579) has been plotted against temperaturein Figure 15 Clearly itmay be positive or negative dependingon the position of the centre of the semicircular arc Variationof the impedance phase angle 120575 = tanminus1 minus (119885

1015840119885

10158401015840) with

frequency plotted on a logarithmic scale is called Bodeplot [23 26] Bode plots at different temperatures have beenshown in Figures 16(a) and 16(b) graphs for 570∘C 573∘Cand 600∘Cbeing given in Figure 16(b) to avoid overlap At lowfrequencies and high temperatures (eg the 700∘C graph)the constant phase part of the phase angle can be seen tobe predominating For a pure capacitor 120575 = minus90

∘ whilefor a resistor it is zero For a capacitor the voltage 119881

119888 lags

behind the response current by 90∘ In the phase angle plotan approach to pure capacitive behavior at low frequencyvalues can usually be identified by 120575 rarr minus90

∘ For an 119877119862

circuit it will have an intermediate value and depends on

120596 as seen in the graph Figure 16(b) contains data sets at119879119898region temperatures and shows a prominent increase of

the phase angle between 1MHz and 55MHz The frequencyranges for near constancy of the phase angle (eg over 20Hzto sim1 kHz for 700∘C) can be observed from the figures Thisconstant phase region appears at low frequencies for the hightemperature runs and at high frequencies for low temperatureruns

DC conductivity has been calculated using the relation[32] 120590dc = (120576

0120576infin)120591 from experimentally found 120591 and

120576infin(= 120576

1015840 value as 119891 rarr infin) Using 120591cross and 120591peak data asfound in Figure 14 temperature dependence of120590dc(cross) and120590dc(peak) and hence that of two sets ofDCactivation energyhave been calculated for the present PNO samples Resultfrom each technique shows expected increase of 120590dc withtemperature (119879) as shown in Figure 17 DC activation energy(119864dc) due to DC conductivity [14] was calculated using theempirical Arrhenius relation 120590dc = 120590

0exp(minus119864dc119896119879) where

119896 is Boltzmann constant 1205900is preexponential factor and 119864dc

is the DC activation energy for the conduction process [33ndash36] by plotting ln(120590dc) versus 1119879 Figure 19 gives this DCactivation energy for different temperature ranges indicatedby the horizontal bars as found independently from 120591crossand 120591peak data for two- and three-region fits Almost allearlier authors determined DC activation energy 119864dc fromrelaxation time via DC conductivity The 2-segment fit hasbeen utilized in the literature for the usual 120591peak-basedevaluation of 119864dc below and above 119879

(Curie)Gonzalez et al [36] calculated relaxation times (120591 =

120591CC 120591119879 120591lowast) and other parameters for PNO sample from their

450∘C to 590∘Cmeasurement of the temperature dependenceof the imaginary dielectric modulus separately by frequencydomain analysis and by time domain analysis Their 120591

lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)

Figure 13 Variation of119885real (real part of impedance) and119885im (imaginary part of impedance) with frequency (plotted in log scale) at differenttemperatures Frequency at the intersection of the two graphs gives a value of the relaxation time of the system to be called 120591cross Relaxationtime estimated from the frequency) at the peaking in 119885

10158401015840 is to be called 120591peak

400 500 600 700

0

200

400

600

800

Temperature (∘C)

120591cross120591peak

Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C

Figure 14 Variation of the relaxation time (120591peak and 120591cross) with temperature (119879) has been shown in one graph relaxation times 120591peak and120591cross being estimated by two different techniques as defined in Figure 13


400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596

Figure 15 Diagrammatic definition of the angle (120579) of Nyquist Plot (in the inset) as detailed in the text and its variation with temperature

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)

Figure 16 (a) Variation of the impedance phase angle 120575 = tanminus1 minus (119885real119885im) with frequency at different temperatures (255∘C 340∘C400∘C 450∘C 500∘C and 700∘C) (b) Variation of the impedance phase angle 120575 = tanminus1 minus (119885real119885im) with frequency at a few importanttemperatures (570∘C 573∘C and 600∘C)

relaxation time due to thermal effect was calculated intime domain using the Kohlrausch-Williams-Watts function119891(119905) = 119890

minus(119905120591lowast

)120573 Finally ⟨120591

119879⟩ the average relaxation time was

calculated using the relation ⟨120591119879⟩ = (Γ(1120573)120573)120591

lowast whereΓ is the Euler gamma function Next 120590dc was calculatedusing the relation 120590dc = 120576

infin⟨120591119879⟩ They made separate

liner fits to their ln(120590dc) versus 1119879 data for data below119879(Curie) and for data above 119879

(Curie) finding however similarvalues 119864dc = 108 eV below 119879

(Curie) and 119864dc = 111 eVabove 119879

(Curie) Finding practically same values apparentlyimplies a single conduction mechanism [36] However the

fact that more than one conduction mechanism is expected[36] from the observed (Figure 2) ldquodeparture of the realpermittivity data froma low frequency plateau-like behaviourtowards the lowest frequencies and high temperaturerdquo hasalso been pointed out by these authors with the commentthat ldquofurther measurements and data treatment to betterelucidate this additional low-frequency effect are in progressrdquoThis motivated us (i) to use 120591cross to find 120590dc and 119864dc and also(ii) to try three segment fitting (Figure 18) as needed for thedata resulting from the 120591cross-based analysisThe data actuallydemands a middle segment (here 570∘C to 600∘C) fit


400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)

120590dc (peak)Ωmiddotmminus1

120590dc

(cro

ss)Ωmiddotmminus1

Figure 17 Variation of DC conductivity 120590dc(crosspeak) with temperature in 400∘C to 700∘C range for quenched PNO sample Here twovalues of DC conductivity 120590dc(cross) = (120576

0120576infin)120591cross in the lower graph and 120590dc(peak) = (120576

0120576infin)120591peak in the upper graph have been calculated

from 120591cross and 120591peak given in Figure 14

minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)

Figure 18 Variation of ln 120590dc(cross) with 1119879(Kminus1) in temperature 400∘C to 700∘C range and least square fitting of the liner equation in threedifferent temperature regions that yield three different values of DC activation energy

Here one notes in Figure 17 that 120590dc(cross) versus 119879 dataclearly fall into three linear segments

400∘C to 565∘C giving (Figure 18) 119864119886

= 10724 plusmn

0043 eV570∘C to 600∘C giving (Figure 18) 119864

119886= 1595 plusmn


119886= 1263 plusmn

0156 eVwhich implies a peaking of the activation energy 119864

119886= 119864dc

(cross) in the Curie temperature (119879119888) region and practically

the same value for low and high temperature regions (ldquoC3rdquodata points in Figure 19) This discovers the expected [36]existence of different 119864dc and hence different conductionmechanisms retaining same or similar values of 119864dc belowand above the 119879

119888region

A 2-segment fit to 120590dc(cross) versus 119879 data of Figure 17yields (ldquoC2rdquo points in Figure 19)

119864119886= 1072 plusmn 0043 eV over 400∘C to 565∘C



119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P

Cross 3Cross 2Peak 3

Figure 19 Activation energy (119864dc) for DC conduction in different temperature regions 119875 in symbol name indicates the use of peak techniqueof finding relaxation time and 119862 indicates the cross technique case Here 2 stands for fit to 2 temperature regions and 3 for 3 temperatureregions fit the chosen temperature region of fit being indicated by corresponding horizontal bar through the symbol

missing the significant rise and fall within a narrow 119879119888region

(570 to 600∘C) to wrongly conclude no significant changeacross 119879

119888(the Curie temperature) This is in line with the

limited knowledge currently available in the literature asalready discussed

120590dc(peak) versus 119879 data of Figure 17 can be seen to havemore scatter than 120590dc(cross) versus 119879 data with the formernot falling well either on a set of straight lines or even on asmooth graph as should be the case from already discussedhigher scatter of 120591peak data We feel that 120591cross should be usedas relaxation time if there is a choice to choose from 120591peak and120591cross data Still we tried linear fits to 120590dc(peak) versus 119879 dataThe 3-segment fit could tackle this scattered data set relativelybetter as follows

400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV

as shown in Figure 19 as ldquoP3rdquo data pointsSo the three-region fits of 120591cross and 120591peak suggest a

peaking in 119864dc versus 119879 variation at or below (resp) theCurie temperatureThis better match of the119864dc peak with theCurie temperature for 120591cross data further supports the betterreliability of 120591cross data Near the transition temperatureDC activation energy is highest (1595 plusmn 0120 eV) a newobservation that needs further verification and explanation

4 ConclusionPresently prepared PbNb

2O6samples revealed pure ortho-

rhombic phase by X-ray Rietveld analysis with confirmationdown to granular level by High Resolution TransmissionElectron Microscopy These structural characterizations aswell as impedance spectroscopy over 20Hz to 55MHz andup to 700∘C established the high quality of these samples

Present evaluations of DC and AC conductivities capac-itance (119862) and resistance (119877) of the equivalent 119862119877 circuitrelaxation times and related activation energies from theanalysis of ourwide-ranging impedance spectroscopy data onorthorhombic PNO and discussions have been either moreextensive than in the literature or done for the first timeThisis the first reporting of the Nyquist diagram the plot of 11988510158401015840versus1198851015840 for orthorhombic leadmetaniobate An impressivepeak (sim760 nF) of the equivalent 119862119877 circuit capacitance (119862)in the119862 versus119879 graph has been obtained at119879

119898as shown AC

conductivity (120590ac) is seen to peak at 119879119898 more prominently in

the higher frequency plots Relaxation time registers a clearpeak at 119879

119898 while falling slowly with increasing temperature

in other temperature regionsMeasured DC electrical conductivity appears to show

three regions of temperature dependence (Figure 17) ratherthan the usually tried ferroelectric and paraelectric regionsA suitably chosen transition region in the plot of ln(120590dc)versus 1119879 in Figure 18 forms the third region interestinglygiving the highest activation energy (Figure 19) A 3-region fitshould be carefully examined for different systems since thethird region may be missed due to data points inadequatewith respect to either the temperature range or the densityof data points or both Moreover a forced two-region fit(C2 points in Figure 19) to data needing a three-regionfit will mask the large up and down (C3 points) of theactivation energy value in the Curie temperature region andindicate a small change of activation energy across the Curietemperature similar to the result of 2-segment fit to timedomain analysis [35] result It appears that the DC activationenergy can be estimated better from 120591cross and 3-segmentfit (Figure 19) unless the result in a particular experimentis against 3-segment fit Presently observed peaking of theactivation energy 119864dc(cross) in the Curie temperature (119879

119888)

region is a new result


The peak at119879119898in the 1205761015840 versus119879 graph is sharp leading to

a value of sim1 for the diffusivity parameter and implying nearabsence of any relaxor property Impedance spectroscopyshowed (Table 1) highest record of ferroelectric-paraelectrictransition temperature (119879

119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574

∘C for 05 kHz This implies potential use ofthis material for piezoelectric sensors and actuators up totemperatures much higher than the limits of BT and PZTbased piezomaterials

Acknowledgments

The dielectric measurement set-up at the Deptartment ofCeramic Engineering NIT Rourkela 769008 India has beenused with the active encouragement of Professor Swadesh KPratihar Authors also thank Shri Pulak Ray and his team atSINP for help in TEM operation U De thanks Alexandervon Humboldt Foundation (Germany) for partial supportthat led to preliminary presentation of a part of this work ininternational conferences and discussions

References

[1] I Ihara ldquoUltrasonic sensing fundamentals and its applicationsto nondestructive evaluationrdquo Lecture Notes Electrical Engineer-ing vol 21 pp 287ndash305 2008

[2] R Kazys A Voleisis and B Voleisiene ldquoHigh temperatureultrasonic transducers reviewrdquo Ultragarsas vol 63 no 2 pp7ndash17 2008

[3] G Goodman ldquoFerroelectric properties of lead metaniobaterdquoJournal of the American Ceramic Society vol 36 no 11 pp 368ndash372 1953

[4] A A Nesterov E V Karyukov and K S Masurenkov ldquoSynthe-sis of phases of composition PbNb

2O6and BaNb

2O6with the

use of active precursorsrdquo Russian Journal of Applied Chemistryvol 82 no 3 pp 370ndash373 2009

[5] R S Rath ldquoUnit-cell data of the lead niobate PbNb206rdquo Acta

Crystallographica vol 10 part 6 pp 437ndash437 1957[6] U De ldquoTEM HT XRD electrical optical and thermal

characterizations of materials for high temperaturepiezoelectric applicationsrdquo in Proceedings of the IUMRS-ICA Abstract no 21 1078 BEXCO Busan Korea 2012httpwwwiumrs-ica2012orgprogramphp

[7] M H Francombe and B Lewis ldquoStructural dielectric andoptical properties of ferroelectric leadmetaniobaterdquo Acta Crys-tallographica vol 11 part 10 pp 696ndash6703 1958

[8] E C Subbarao and G Shirane ldquoNonstoichiometry and ferro-electric properties of PbNb

2O6-type compoundsrdquo The Journal

of Chemical Physics vol 32 no 6 pp 1846ndash1851 1960[9] E C Subbarao ldquoX-ray study of phase transitions in ferroelec-

tric PbNb2O6and related materialsrdquo Journal of the American

Ceramic Society vol 43 no 9 pp 439ndash442 1960[10] S Ray E Gunter and H J Ritzhaupt-Kleissl ldquoManufactur-

ing and characterization of piezoceramic lead metaniobatePbNb

2O6rdquo Journal of Materials Science vol 35 no 24 pp 6221ndash

6224 2000[11] K R Chakraborty K R Sahu A De and U De ldquoStruc-

tural characterization of orthorhombic and rhombohedral leadmeta-niobate samplesrdquo Integrated Ferroelectrics vol 120 no 1pp 102ndash113 2010

[12] K R Sahu andUDe ldquoThermal characterization of piezoelectricand non-piezoelectric leadmeta-niobaterdquoThermochimica Actavol 490 no 1-2 pp 75ndash77 2009

[13] F Guerrero Y Leyet M Venet J de Los and J A EirasldquoDielectric behavior of the PbNb

2O6ferroelectric ceramic in

the frequency range of 20Hz to 2GHzrdquo Journal of the EuropeanCeramic Society vol 27 no 13ndash15 pp 4041ndash4044 2007

[14] S K Barbar and M Roy ldquoSynthesis structural electrical andthermal studies of Pb

1minus119909Ba119909Nb2O6(x = 00 and 04) ferroelec-

tric ceramicsrdquo ISRN Ceramics vol 2012 Article ID 710173 5pages 2012

[15] J W Griffin T J Peters G J Posakony H T Chien and L JBond Under-Sodium Viewing A Review of Ultrasonic ImagingTechnology for Liquid Metal Fast Reactors PNNL-18292 USDepartment of Energy Pacific Northwest National LaboratoryRichland Wash USA 2009

[16] I V Kityk M Makowska-Janusik M D Fontana M Aillerieand A Fahmi ldquoInfluence of non-stoichiometric defects onoptical properties in LiNbO

3rdquo Crystal Research and Technology

vol 36 no 6 pp 577ndash589 2001[17] M Venet A Vendramini F L Zabotto F D Garcia and J

A Eiras ldquoPiezoelectric properties of undoped and titaniumor barium-doped lead metaniobate ceramicsrdquo Journal of theEuropean Ceramic Society vol 25 no 12 pp 2443ndash2446 2005

[18] H S Lee and T Kimura ldquoEffects of microstructure on thedielectric and piezoelectric properties of lead metaniobaterdquoJournal of theAmericanCeramic Society vol 81 no 12 pp 3228ndash3236 1998

[19] J Soejima K Sato and K Nagata ldquoPreparation and charac-teristics of ultrasonic transducers for high temperature usingPbNb

2O6rdquo Japanese Journal of Applied Physics 1 vol 39 no 5

pp 3083ndash3085 2000[20] Y M Li L Cheng X Y Gu Y P Zhang and R H Liao

ldquoPiezoelectric and dielectric properties of PbNb2O6-based

piezoelectric ceramics with high Curie temperaturerdquo Journal ofMaterials Processing Technology vol 197 no 1ndash3 pp 170ndash1732008

[21] P Q Mantas ldquoDielectric response of materials extension to theDebye modelrdquo Journal of the European Ceramic Society vol 19no 12 pp 2079ndash2086 1999

[22] S Zhang C A Randall and T R Shrout ldquoHigh Curietemperature piezocrystals in the BiScO

3-PbTiO

3perovskite

systemrdquo Applied Physics Letters vol 83 no 15 pp 3150ndash31522003

[23] J R Macdonald and W B Johnson in Impedance SpectroscopyTheory Experiment and Applications E Barsoukov and J RMacdonald Eds John Wiley amp Sons Hoboken NJ USA 2ndedition 2005

[24] S Sen and R N P Choudhary ldquoImpedance studies of Srmodified BaZr

05Ti095

O3ceramicsrdquo Materials Chemistry and

Physics vol 87 no 2-3 pp 256ndash263 2004[25] A Shukla R N P Choudhary and A K Thakur ldquoThermal

structural and complex impedance analysis of Mn4+ modifiedBaTiO

3electroceramicrdquo Journal of Physics and Chemistry of

Solids vol 70 no 11 pp 1401ndash1407 2009[26] K Uchino and S Nomura ldquoCritical exponents of the dielectric

constants in diffused phase transition crystalsrdquo FerroelectricsLetters Section vol 44 no 11 pp 55ndash61 1982

[27] L E Cross ldquoRelaxor ferroelectricsrdquo Ferrooelectrics vol 76 no1 pp 241ndash267 1987


[28] O Raymond R Font N Suarez-Almodovar J Portelles andJ M Siqueiros ldquoFrequency-temperature response of ferroelec-tromagnetic Pb (Fe

12Nb12)O3ceramics obtained by different

precursorsmdashpart I structural and thermo-electrical character-izationrdquo Journal of Applied Physics vol 97 no 8 Article ID084107 8 pages 2005

[29] B Behera E B Arajo R N Reis and J D S Guerra ldquoAC con-ductivity and impedance properties of 065Pb(Mg

13Nb23)O3-

035 PbTiO3ceramicsrdquo Advances in Condensed Matter Physics

vol 2009 Article ID 361080 6 pages 2009[30] R N P Choudhary D K Pradhan G E Bonilla and R S

Katiyar ldquoEffect of La-substitution on structural and dielectricproperties of Bi(Sc

12Fe12)O3ceramicsrdquo Journal of Alloys and

Compounds vol 437 no 1-2 pp 220ndash224 2007[31] K S Rao D M Prasad P M Krishna and J H Lee ldquoSynthesis

electrical and electromechanical properties of tungsten-bronzeceramic oxide Pb

068K064

Nb2O6rdquo Physica B vol 403 pp 2079ndash

2087 2008[32] Z Lu J P Bonnet J Ravez and P Hagenmuller ldquoCorrela-

tion between low frequency dielectric dispersion (LFDD) andimpedance relaxation in ferroelectric ceramic Pb

2KNb4TaO15rdquo

Solid State Ionics vol 57 no 3-4 pp 235ndash244 1992[33] P S Sahoo A Panigrahi S K Patri and R N P Choudhary

ldquoImpedance spectroscopy of Ba3Sr2DyTi3V7O30ceramicrdquo Bul-

letin of Materials Science vol 33 no 2 pp 129ndash134 2010[34] S Rachna S M Gupta and S Bhattacharyya ldquoImpedance

analysis of Bi325

La075

Ti3O12

ferroelectric ceramicrdquo Pramanavol 71 no 3 pp 599ndash610 2008

[35] S Devi and A K Jha ldquoDielectric and complex impedancestudies of BaTi

085W015

O3+120575

ferroelectric ceramicsrdquo Bulletin ofMaterials Science vol 33 no 6 pp 683ndash690 2010

[36] R L Gonzalez Y Leyet F Guerrero et al ldquoRelaxation dynamicsof the conductive process for PbNb

2O6ferroelectric ceramics in

the frequency and time domainrdquo Journal of Physics CondensedMatter vol 19 no 13 Article ID 136218 2007

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


[5 6] that the orthorhombic PNO (ferroelectric) changes to atetragonal structure (paraelectric) above sim570∘C

Goodman [3] had earlier concluded the 119879(Curie) of

quenched PNO to be 570∘C from their dilatometric anddielectric characterizations Although this temperature isregarded even in recent papers [10] as the Curie temperatureof PbNb

2O6 almost all the recent electrical measurements

have obtained much lower values of its Curie temperature(Table 1) Reference [10] quoted 119879

(Curie) of 500∘C for Ferro-

perm (Denmark) PNO samples (1995) and 495∘C forMorganMatroc (UK) PNO samples (1997) Lower 119879

(Curie) in thesecommercial samples may or may not be due to efforts tooptimize other piezoelectric parameters Table 1 has beencompiled from recent publications It shows 119879

(Curie) to be inthe range 517∘C to 540∘C only except in present samplesSo there is a need to optimize preparation conditions ofquenched PbNb

2O6to get highest possible Curie tempera-

ture high purity and high density A pointer in this directionis our observation on quenched PNO [11] of an endothermicsignal at 5706∘C in Differential Scanning Calorimetry [12]

Here our preparation of high quality orthorhombic PNOand results of our impedance spectroscopy up to 700∘C andover a wide frequency range from 20Hz to 55MHz witha detailed analysis have been presented Intrinsic cationicdefects in niobates like LiNbO

3and their role are well known

[16] Likely lattice defects in a quench-prepared PbNb2O6

sample should similarly be regarded as an intrinsic part ofthe sample The structure of the samples has therefore beencharacterized fully before other studies Although some workon PNO (Table 1) and a few on various targeted chemicalsubstitutions in PNOhave been reported in the literature notall possible dielectric and electrical parameters for PNO itselfhave yet been derived from IS data This has been attemptedhere The dielectric response in such an electroceramic isknown to be complex with many contributions that need tobe known and understood So desirable observations likethe highest 119879

(Curie) as well as all uncommon observations ofthe present work are reproduced All possible data analysishas been carried out yielding important parameters like bulkresistance relaxation times activation energies AC and DCconductivity and phase angle

2 Materials and Methods

Aldrich lead(II) oxide (PbO 99999 yellowish orange andMelting Point = 886∘C) and niobium pentoxide (999 GR)of Loba Chemie weighed in proper proportion to givePb Nb = 1 2 plus 2 of excess PbO have been well groundunder isopropyl alcohol dried and pelletized Additions ofexcess PbO were introduced by some earlier workers tocompensate possible evaporative loss of PbO To get bestPbNb

2O6 present firings have been done in stages at 1050∘C

1290∘C and 1270∘C in a box furnace with PID temperaturecontroller Extra PbO (3) has been added before the 3rdfiring All our firings have been done in palletized form toprovide intimate contact and reduce Pb loss But grindingand repalletizing at each step have also been undertakento improve mixing and the sample quality After the last

Table 1 Comparison of recently reported Curie temperatures oforthorhombic PbNb2O6 samples

Sample SinteringCurie temperature 119879

(Curie) in∘CTemp

(∘C)Time(h)

Present 1270 45 119879(Curie) gt 576 for 40MHz and

gt574 for 05 kHz[17] 1270 45 517[18] 1270 mdash 534 and 540 (both at 10 kHz)[19] mdash mdash 540 (presumably at 80 kHz)[20] 1240ndash1260 4 530 (at 10 kHz)

[13] 1270 45 531 (at 1 kHz) 528 (at 1MHz) and533 (at 10MHz)

firing the samples have been quenched The samples havebeen characterized by XRD with Rietveld analysis [11] andTransmission Electron Microscopy (TEM)

The impedance spectroscopy has been carried out usingSolatron ldquoSI 1260 Impedance Gain Phase Analyzerrdquo with ahigh temperature attachment Our PNO pellets (diametersim12mm and 22 to 24mm thick) have not been poled beforemeasurement Silver paint coat on the flat faces of the pelletunder study served as the electrodes for IS measurementsThis measurement of 120576

1015840 and 120576

10158401015840 (the real and imaginarycomponents respectively of the relative dielectric constantie permittivity) has been done for different measuringfrequencies at different values the sample temperature (119879)while heating from room temperature to 700∘C

3 Results and Discussion

XRD pattern and Rietveld analysis [11] Figure 1(a) con-firmed the orthorhombic structure and absence of any otherphase The smallness of the difference of the fitted graphand raw data proved our Rietveld fit to be good It yields119886 = 176468(7) A 119887 = 179512(7) A and 119888 = 38704(1) AThe samples showed about 80 of the theoretical densityon average TEM diffractograms [6] with the electron beamon individual grains of the ceramic sample always gavediffraction patterns that matched these lattice parametersfrom XRD result One TEM diffraction pattern is shown inFigure 1(b) This way all of the nearly forty grains examinedhave been found to be in orthorhombic phase

Figures 2ndash4 show 120576

1015840 versus frequency 120576

10158401015840 versus fre-quency and tan 120575 = 120576

10158401015840120576

1015840 versus frequency results (over20Hz to 55MHz range) for 12 temperatures from 50∘Cto 700∘C In Figure 2 real part (1205761015840) of dielectric constantdecreases with increase of measuring frequency up to aboutln119891 = 12 to 14 region implying sim162 kHz to sim1203 kHzregion and then increases sharply with increase of fre-quency as reported earlier [13] for all temperatures exceptat low temperatures like 200∘C Moreover 1205761015840 is low and lessdependent on frequency at low temperatures up to 300∘Cleading to overlap of several graphs It increases with increaseof temperature up to 573∘C Graph of 120576

1015840 shows signifi-cantly increased values in the 573∘C graphs with respect to


10 20 30 40 50 60 70 80minus2000

minus1000

0

1000

2000

3000

4000

5000

6000

X-ra

y in

tens

ity (a

u)



(a) (b)



3 4 5 6 7 8 9 10 11 12 13 14 15 16

0

2000

4000

6000

8000

10000

12000

6 8 10 12 14 160120576998400

1

2

3

4times103

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)


2O6










10158401015840 at ln119891 =




10158401015840120576


1015840










3 4 5 6 7 8 9 10 11 12 13 14 15

0

10 11 12 13 14 15 16

0

times102times105

2

4

6

8

10

12 5

4

3

2

1

120576998400998400

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)




4 6 8 10 12 14 16

0

20

40

60

80

100

120

10 11 12 13 14 150

02

04

06

08

1

Die

lect

ric lo

ss (t

an120575

)

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)


2O6


1015840


119898with 119879

119898




10158401015840 in the 120576







100 200 300 400 500 600 7000

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

250 300 3500

100

200

300 560 580 600 620 640

1000

2000

3000

4000

PNQ



Temperature (∘C)

120576998400


2O6

100 200 300 400 500 600 70005

10152025303540455055


0018036054072

09108

500 550 6000

044088132176

22264308352396

500 kHz

4 MHz3 MHz

50 kHz


Temperature (∘C)

tan120575






1015840The 119885

10158401015840 versus 119885





times103

12

10

8

6

4

0

2

120576998400m

ax


2O6

0 200 k 400 k 600 k 800 k

0

200 k

400 k

600 k

800 k

010

M20

M30

M40

M

020 M40 M60 M80 M

100 M120 M

120596

Temperature (∘C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

500∘C550∘C570∘C573∘C

600∘C

200∘C

650∘C700∘C

(a)

0 1 M 2 M 3 M 4 M 5 M 6 M 7 M

0

1 M

2 M

3 M

4 M

5 M

6 M

7 M

Temperature ( C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

120596

400∘C440∘C460∘C480∘C

(b)



119885







119885



10158401015840= 1198772 = 119885




400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600


Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C


2O6sample plotted


1015840 and 119885





1015840-axis again at 1198770 119877 = (119877




0can be determined




1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is




1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862


1015840







0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10




Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840



0exp (minus119864ac119896119879)


119888) is due to





0=


10


(with 1205900


0= 6253 times 10



1015840 and 119885imaginary = 119885


1015840 and 119885



15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




10 20 30 40 50 60 70 80minus2000

minus1000

0

1000

2000

3000

4000

5000

6000

X-ra

y in

tens

ity (a

u)



(a) (b)



3 4 5 6 7 8 9 10 11 12 13 14 15 16

0

2000

4000

6000

8000

10000

12000

6 8 10 12 14 160120576998400

1

2

3

4times103

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)


2O6










10158401015840 at ln119891 =




10158401015840120576


1015840










3 4 5 6 7 8 9 10 11 12 13 14 15

0

10 11 12 13 14 15 16

0

times102times105

2

4

6

8

10

12 5

4

3

2

1

120576998400998400

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)




4 6 8 10 12 14 16

0

20

40

60

80

100

120

10 11 12 13 14 150

02

04

06

08

1

Die

lect

ric lo

ss (t

an120575

)

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)


2O6


1015840


119898with 119879

119898




10158401015840 in the 120576







100 200 300 400 500 600 7000

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

250 300 3500

100

200

300 560 580 600 620 640

1000

2000

3000

4000

PNQ



Temperature (∘C)

120576998400


2O6

100 200 300 400 500 600 70005

10152025303540455055


0018036054072

09108

500 550 6000

044088132176

22264308352396

500 kHz

4 MHz3 MHz

50 kHz


Temperature (∘C)

tan120575






1015840The 119885

10158401015840 versus 119885





times103

12

10

8

6

4

0

2

120576998400m

ax


2O6

0 200 k 400 k 600 k 800 k

0

200 k

400 k

600 k

800 k

010

M20

M30

M40

M

020 M40 M60 M80 M

100 M120 M

120596

Temperature (∘C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

500∘C550∘C570∘C573∘C

600∘C

200∘C

650∘C700∘C

(a)

0 1 M 2 M 3 M 4 M 5 M 6 M 7 M

0

1 M

2 M

3 M

4 M

5 M

6 M

7 M

Temperature ( C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

120596

400∘C440∘C460∘C480∘C

(b)



119885







119885



10158401015840= 1198772 = 119885




400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600


Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C


2O6sample plotted


1015840 and 119885





1015840-axis again at 1198770 119877 = (119877




0can be determined




1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is




1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862


1015840







0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10




Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840



0exp (minus119864ac119896119879)


119888) is due to





0=


10


(with 1205900


0= 6253 times 10



1015840 and 119885imaginary = 119885


1015840 and 119885



15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




3 4 5 6 7 8 9 10 11 12 13 14 15

0

10 11 12 13 14 15 16

0

times102times105

2

4

6

8

10

12 5

4

3

2

1

120576998400998400

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)




4 6 8 10 12 14 16

0

20

40

60

80

100

120

10 11 12 13 14 150

02

04

06

08

1

Die

lect

ric lo

ss (t

an120575

)

50∘C100∘C200∘C300∘C

400∘C500∘C550∘C570∘C

573∘C600∘C650∘C700∘C

ln 119891 (Hz)


2O6


1015840


119898with 119879

119898




10158401015840 in the 120576







100 200 300 400 500 600 7000

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

250 300 3500

100

200

300 560 580 600 620 640

1000

2000

3000

4000

PNQ



Temperature (∘C)

120576998400


2O6

100 200 300 400 500 600 70005

10152025303540455055


0018036054072

09108

500 550 6000

044088132176

22264308352396

500 kHz

4 MHz3 MHz

50 kHz


Temperature (∘C)

tan120575






1015840The 119885

10158401015840 versus 119885





times103

12

10

8

6

4

0

2

120576998400m

ax


2O6

0 200 k 400 k 600 k 800 k

0

200 k

400 k

600 k

800 k

010

M20

M30

M40

M

020 M40 M60 M80 M

100 M120 M

120596

Temperature (∘C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

500∘C550∘C570∘C573∘C

600∘C

200∘C

650∘C700∘C

(a)

0 1 M 2 M 3 M 4 M 5 M 6 M 7 M

0

1 M

2 M

3 M

4 M

5 M

6 M

7 M

Temperature ( C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

120596

400∘C440∘C460∘C480∘C

(b)



119885







119885



10158401015840= 1198772 = 119885




400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600


Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C


2O6sample plotted


1015840 and 119885





1015840-axis again at 1198770 119877 = (119877




0can be determined




1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is




1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862


1015840







0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10




Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840



0exp (minus119864ac119896119879)


119888) is due to





0=


10


(with 1205900


0= 6253 times 10



1015840 and 119885imaginary = 119885


1015840 and 119885



15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




100 200 300 400 500 600 7000

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

250 300 3500

100

200

300 560 580 600 620 640

1000

2000

3000

4000

PNQ



Temperature (∘C)

120576998400


2O6

100 200 300 400 500 600 70005

10152025303540455055


0018036054072

09108

500 550 6000

044088132176

22264308352396

500 kHz

4 MHz3 MHz

50 kHz


Temperature (∘C)

tan120575






1015840The 119885

10158401015840 versus 119885





times103

12

10

8

6

4

0

2

120576998400m

ax


2O6

0 200 k 400 k 600 k 800 k

0

200 k

400 k

600 k

800 k

010

M20

M30

M40

M

020 M40 M60 M80 M

100 M120 M

120596

Temperature (∘C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

500∘C550∘C570∘C573∘C

600∘C

200∘C

650∘C700∘C

(a)

0 1 M 2 M 3 M 4 M 5 M 6 M 7 M

0

1 M

2 M

3 M

4 M

5 M

6 M

7 M

Temperature ( C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

120596

400∘C440∘C460∘C480∘C

(b)



119885







119885



10158401015840= 1198772 = 119885




400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600


Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C


2O6sample plotted


1015840 and 119885





1015840-axis again at 1198770 119877 = (119877




0can be determined




1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is




1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862


1015840







0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10




Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840



0exp (minus119864ac119896119879)


119888) is due to





0=


10


(with 1205900


0= 6253 times 10



1015840 and 119885imaginary = 119885


1015840 and 119885



15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





times103

12

10

8

6

4

0

2

120576998400m

ax


2O6

0 200 k 400 k 600 k 800 k

0

200 k

400 k

600 k

800 k

010

M20

M30

M40

M

020 M40 M60 M80 M

100 M120 M

120596

Temperature (∘C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

500∘C550∘C570∘C573∘C

600∘C

200∘C

650∘C700∘C

(a)

0 1 M 2 M 3 M 4 M 5 M 6 M 7 M

0

1 M

2 M

3 M

4 M

5 M

6 M

7 M

Temperature ( C)

119885real (Ω)

minus119885

imag

inar

y(Ω

)

120596

400∘C440∘C460∘C480∘C

(b)



119885







119885



10158401015840= 1198772 = 119885




400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600


Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C


2O6sample plotted


1015840 and 119885





1015840-axis again at 1198770 119877 = (119877




0can be determined




1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is




1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862


1015840







0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10




Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840



0exp (minus119864ac119896119879)


119888) is due to





0=


10


(with 1205900


0= 6253 times 10



1015840 and 119885imaginary = 119885


1015840 and 119885



15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




400 450 500 550 600 650 700

0

1

2

3

26

28

30

0

200

400

600


Capa

cita

nce (

nF)

Temperature (∘C)

Bulk

resis

tanc

e (M

Ω) 5737∘C


2O6sample plotted


1015840 and 119885





1015840-axis again at 1198770 119877 = (119877




0can be determined




1015840

max) = (119879 minus 119879119898)120574119862119908 where 119862

119908is




1015840

max) =

120574 ln(119879 minus 119879119898) minus ln119862


1015840







0120576

1015840 tan 120575 = 21205871198911205760120576

10158401015840 where 1205760= 10

74120587119888

2= 8845 times

10




Frequency (Hz) 119879119898(∘C) 119862

119908times 10

5 (∘C) 120574 120576

1015840



0exp (minus119864ac119896119879)


119888) is due to





0=


10


(with 1205900


0= 6253 times 10



1015840 and 119885imaginary = 119885


1015840 and 119885



15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




15 2 25 3 35 4 45 5minus12

minus11

minus10

minus9

minus8

minus7

minus6

3 MHz2 MHz 1 MHz

50 kHz 1 kHz

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(a)

15 2 25 3 35 4 45 5

minus11

minus10

minus9

minus8

minus7

minus6

50 kHz

119862 = 12356904∘C120574 = 10346 and

ln (1

120576998400minus1120576998400 m

ax)

ln (119879 minus 119879119898)

(b)





1015840



1 15 2 25 3 35minus20

minus18

minus16

minus14

minus12

minus10

minus8

minus6

minus4

minus2

0


10 kHz1 kHz05 kHz

1000119879 (Kminus1)

ln120590

ac(Ωmiddotmminus1)

120596

5755∘C


2O6


lowast= 119877(1 + 119895120596119877119862) = 119885

1015840minus

119895119885



10158401015840= 1198772 and 119885

1015840= 1198772 So




1015840= 119885




00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





00306091215

Frequency (Hz)

119864119886

(eV

)

times106

50∘C to 300∘C400∘C to 550∘C580∘C to 700∘C





10158401015840 peak of 119885




0

since 119877infin



1015840119885

10158401015840) with



119888 lags


∘ For an 119877119862






120576infin(= 120576








lowast


0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0

0005

001

0015

002

0

05

1

15

2

25

0

002

004

006

008

01

0

005

01

015

02

119885im

119885im

119885im119885im

119885im

119885re

al

119885real

119885real

119885real

119885real

(M Ω

)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

119885im

119885re

al(M

Ω)

101 102 103 104 105 106 107

101 102 103 104 105 106 107101 102 103 104 105 106 107

101 102 103 104 105 106 107

120591 = 3229 120583s

120591 = 240281 120583s

120591 = 42412120583s

120591 = 72218 120583s

700∘C 450∘C

600∘C 570∘C

log 119891 (Hz) log 119891 (Hz)

log 119891 (Hz)log 119891 (Hz)



400 500 600 700

0

200

400

600

800

Temperature (∘C)


Rela

xatio

n tim

e120591

(120583s)

5747∘C

5747∘C



400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




400 450 500 550 600 650 700 750minus80

minus60

minus40

minus20

0

20

40

60

80

100

0 5 10minus10

minus5

0

5

10

Angle

Ang

le (120579

∘)

Temperature (∘C)

minus119885

im119877120572

119885real

1198770

(1198830 1198840)119903 120579

120596


0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

Impe

denc

e pha

se an

gle120575

101 102 103 104 105 106 107

log 119891 (Hz)400∘C500∘C700∘C

255∘C340∘C450∘C

(a)

0

minus10

minus20

minus30

minus40

minus50

minus60

minus70

minus80

minus90

minus100

101 102 103 104 105 106 107

log 119891 (Hz)

Impe

denc

e pha

se an

gle120575

570∘C573∘C600∘C

(b)




)120573 Finally ⟨120591











400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




400 500 600 700

0

1

2

3

0

23

46

Temperature (∘C)

400 500 600 700Temperature (∘C)

120590dc (cross)

times10minus3

times10minus4

120590dc

(pea

k)


120590dc

(cro

ss)Ωmiddotmminus1





minus8

minus9

minus10

minus11

minus12

minus13

minus14

1 11 12 13 14 151000119879 (Kminus1)

ln120590

dc(Ωmiddotmminus1)

120590dc (cross)




= 10724 plusmn


119886= 1595 plusmn


119886= 1263 plusmn


119886= 119864dc



119888region





119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




119864119886

(eV

)

16

14

12

1

Temperature (∘C)400 450 500 550 600 650 700

C

C

C

C

C

CCP

P

P

P








400∘C to 480∘C 119864119886= 1028 plusmn 0101 eV

500∘C to 590∘C 119864119886= 1523 plusmn 0130 eV

600∘C to 700∘C 119864119886= 1387 plusmn 0168 eV







119898as shown AC






119888)





119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






119898) 119879119898

gt 580

∘C for 55MHz and119879119898

gt 574


Acknowledgments


References





2O6and BaNb

2O6with the



































3-PbTiO

3perovskite




05Ti095













13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials








13Nb23)O3-







068K064




2KNb4TaO15rdquo




analysis of Bi325

La075

Ti3O12



085W015

O3+120575












CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


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Research Article Dielectric Properties of PbNb 2 O 6 up to...

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