piezoelectric, piezoceramics, lead-free, Pb-free, actuator, element, ceramics, transducer, effects, PZT

Ferroelectric Properties of Lead-Free (Pb-free) Piezoelectric Ceramics

presented by Dr. Kusumoto at Japan.

> I hope that practical piezoelectric ceramic materials are developed for saveing the enviroment

by sharing of information about lead-free piezoelectric ceramic materials.

< Contents >-------------------------------------------------------------------------------

1. Table. List of Pr of compounds for lead-free ( Pb-free ) piezoelectric ceramics

2. Table. List of candidates for lead-fee piezoelectric ( Pb-free ) ceramic materials.

3. Representative refferenceies related to lead-free ( Pb-free ) piezoceramics.

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1. TABLE. List of Pr of Lead-Free Piezoelectric Ceramics.

< Note, C/m2 = mC/cm2 = 1000mC/m2 >

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--------Compounds-------Curie temp.------( Tc, deg.C. )--------Pr, ( mC/cm2 ) ---------Others

----------------------------------------------------------------------------------------------------------------------

No.1. LiNbO3 , 1210 deg.C., 10 iferroelectric > paraelectric) , (m.p.1253 deg.C) , about 70 (at R.T )

(Triclinic), Psudo-Ilmenite structure, Not perovskite structure

(ASTM card hexagonal , ahex=5.1494, chex=13.8620) , dielectric const.=6000 at about 1200 deg.C.

No.2. PbTiO3 ( for refferenc) , 490 deg.C., 57 ( 23 deg. C.) (tetragonal) , a=0.3896, c=0.4136nm (c/a=1.06),

Displacive-type ferroelectrics

------------------75(Single crystal) , Rhomb. => , ? deg.C. => Tetragonal => 490 deg.C. => Cubic,

dielectric const.=4000 at 490 deg.C.

No.3. LiTaO3 , 665 deg.C. , 5 (ferroelectric > paraelectric) , (m.p 1650 deg.C), about 50( at R.T)(Triclinic)

Psudo-Ilmenite structure, Not perovskite structure ahex=0.515428, chex=1.378351nm,

dielectric const.=2000 at 660 deg.C.

No.4. PZT (for refference) , 350 deg.C., 40mC/cm2, Mixed crystal (Rhomb.+Tetragonal )

------Kp=0.53, dielectric const.=1500 at 420 deg.C. (PT/PZ=50/50)

No.5. Bi0.5Na0.5TiO3 ( BNT ) , 320 deg.C., a=0.3891nm , 38mC/cm2

-------Rhomb. ( at R.T ) Ferro.=> 200 deg.C. => Anti-ferro. , Single crystal? Ec=7.3kV/mm Poling difficulut ,

Kp=0.15 , dielectric const. = 2400 at 320 deg.C.

-------(High purity ceramics, Ec=5.9kV/mm, Pr = 33.7 ) ( Normal purity ceramics Ec=3.1kV/mm, Pr=26.5 )

No.6. (Na0.5K0.5)NbO3 , 420 deg.C. , 33mC/cm2 , Kp=0.45? , Ortho.( at R.T. ) => 200 deg.C. => Tetragonal => 420 deg.C.=> Cubic

No.7. 0.97(Bi0.5Na0.5)TiO3-0.03NaNbO3 BNTN-3) about 300 deg.C. , 32.6mC/cm2 , K33=0.43 , Kp=0.1 or more

--------Relaxor ferroelectrics, Ec=5kV/mm, d33=71x10-12C/N

No.8. BaTiO3 , 135 deg.C.(m.p. deg.C.) , 26(23 deg.C) , Tetragonal ( c/a=1.01 ) a=0.3989,c=0.4029nm,

Kp=0.35, Displacive-type ferroelectrics

Rhomb.iŽO• ) =>-70 deg.C.) => Ortho.=>5 deg.C. ) => Tetragonal => 135 deg.C. => Cubic,

dielectric const.=5000-8000 at 135 deg.C.

No.9. Bi4Ti3O12 (m=3) (BIT) , 680 deg.C.675 deg.C. , 0.87 , BLSF, d33=20x10-12C/N,

-------------------On single crystal, a-axis direction 2Pr=100 mC/cm2)

Ceramics > Pr=12 mC/cm2, Ceramics doped W > 2Pr=41 mC/cm2

BIT+La and Nd > Pr=20mC/cm2 or more.

No.10. KNbO3 , Ferroelectrics , 435 deg.C. (m.p.1039 deg.C.) , 0.9 (23 deg.C. ) 30 (250 deg.C.)( Orthorhombic)

Simple perovskite structure, LaAlO3-type compounds , Sintering difficultH

Rhomb.=>(-10 deg.C.) => Ortho.=> 225 deg.C. => Tetragonal => 435 deg.C.=> Cubic , a=0.5697,b=0.3971, c=0.5720nm

>K33=0.66(Single crystal)

No.11. (Na0.86Li0.14)NbO3 , 400 deg.C. , 15? mC/cm , Monoclinic => 20 deg.C. => Tetragonal => 400 deg.C. => Psudo-Cubic , Kp=0.23 -,

dielectric const. = 2000 at 400 deg.C.

No.12. SrBi2(V,Nb)2O9 (SBV-SBN, SBVN) , 456 deg.C., 8mC/cm2 , Sintering temp. 1150 deg.C. , BLSF

No.13. SrBi2Ta2O9 (SBTa, SBT) (m=2) , 335 deg.C.310 deg.C.?) , 0.86 , Sintering temp.=1300 deg.C. , BLSF , d33=23x10-12C/N , 7mC/cm2

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2. TABLE. List of Candidates for Lead-Free Piezoelectric Ceramic Materials.

< Note, C/m2 = mC/cm2 = 1000mC/m2 >

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Compounds , Curie Temp., ( deg .C ) , Pr , Crystal-system at R.T. , Others

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< Simple and Complex Perovskite >

PZT (for refference ) , 350 deg.C., 40mC/cm2 , Mixed crystal ( Tetragonal and Rhomb. phase )

PbTiO3 ( for refference ) , 490 deg.C., 57(at 23 deg.C.) , (tetragonal) , a=0.3896 , c=0.4136nm (c/a=1.06),

Displacive-type ferroelectrics , 75(at Single crystal , Rhomb. => ? deg.C. => Tetragonal =>(490 deg.C.) => Cubic

CdTiO3 (for refference ) -193? deg.C., Pnma (at R.T) Ortho.

BaTiO3 , 135 deg.C. (m.p = ?) 26 ( at 23 deg.C. ) , Tetragonal a=0.3989,c=0.4029nm (c/a=1.01),

Displacive-type ferroelectrics, Rhomb.=>(-90 deg.C.) => Ortho.=>(5 deg.C.) => Tetragonal => (135 deg.C.) => Cubic

(Ba,Sr)(Ti,Al)O3

BaTiO3-BiMnO3

BaTiO3-BiFeO3

BaTiO3-BiScO3 [BaTiO3-(Bi2O3-Sc2O3)]

CaTiO3 , (m.p.= 2100 deg.C. , Ortho. , GdFeO3-type compounds, a=0.53670,b=0.54439, c=0.76438nm,

Simple perovskite structure, Ortho. =>(1260 deg.C.) => Cubic, Not ferroelectrics, Quantum paraelectrics

Ca1-xLa2x/3TiO3

Ca1-xNd2x/3TiO3

(Ca0.25Cu0.75)TiO3 , distorted perovskite

BaTiO3-SrTiO3 , Ferroelectrics at very low temp.

0.92BaTiO3-0.08CaTiO3, Kp=0.25

SrTiO3 , -163 (m.p.= about 2000 deg.C.) cubic at R.T, a=0.3904nm, Quantum paraelectrics,

Simple perovskite structure , Tetragonal =>(-163 deg.C.) => Cubic

La2/3TiO3

(La0.5Li0.5)TiO3 , ?

(Nd0.5Li0.5)TiO3

(Dy1/3Nd1/3)TiO3

ScTiO3 , ?

CeTiO3 , ?

GdTiO3 , ?

YTiO3 , ?

(Bi0.5Na0.5)TiO3 , BNT) , 320 deg.C., a=0.3891nm , 38mC/cm2 , Rhomb.(at R.T.),

Ferroelectrics => 200 deg.C. => Anti-ferroelectrics, Ec=7.3kV/mm , Poling difficult?

(Bi0.5K0.5)TiO3 (BKT) , 380 deg.C., Ferroelectrics a=0.3918nm, c=0.4013nm, c/a=1.0242

(Bi0.5Ag0.5)TiO3, BAT) , Is there?

(Bi0.5Li0.5)TiO3 , BLiT) pyrochlore structure

(Nd1/2Na1/2)TiO3

(Y1/2Na1/2)TiO3 , a = 0.53nm, c= 0.54 nm, Sintering temp.= 1250 deg.C.

(Er1/2Na1/2)TiO3 , a= 0.53nm, c= 0.54 nm, Sintering temp.= 1250 deg.C.

(Tm1/2Na1/2)TiO3 , a= 0.53nm, c= 0.54 nm, Sintering temp.= 1250 deg.C.

(Yb1/2Na1/2)TiO3 , a= 0.53nm, c= 0.54 nm, Sintering temp.= 1250 deg.C.

PbZrO3 <for refference> monoclinic, a=0.4158, b=0.4110nm

BaZrO3 , - (m.p.=?) , Cubic perovskite , a=0.4192nm

CaZrO3 , Ortho. , PDF No.35-790 a=0.575, b=0.801, c=0.559nm

SrZrO3 , Ortho. , PDF No.44-161 a=0.5818, b=0.8204, c=0.5797nm

BaZnO3

BaNbO3

Ba(ZnxNb1-x)O3

0.7BaTiO3-0.3BaZrO3 (BTZ) , -42 deg.C., Psudo-cubic , (Dielectric constants = 22000)

0.95BaTiO3-0.05BaZrO3 (BTZ) , 110 deg.C., Monoclinic at R.T

Monoclinic(F) => ( 55 deg.C.) => Tetragonal(F) => (110 deg.C.) => Cubic(<= Low Tc)

BaTi0.91(Hf0.5Zr0.5)0.09O3 , Tc=about 90 deg.C., Dielectric constants=14000 at Tc

SrSnO3 , ? , PDF No.22-1442

CaSnO3 , ? , Tin oxide calcium PDF No.31-317

BaSnO3 , - , Cubic , a=0.4117nm

BaMoO3 , - , Cubic , a=0.4040nm

BaPrO3 , Orthohombic a=0.6213, b=0.6189, c=0.8732nm

BaHfO3

BaBiO3 , ? , Monoclinic at R.T, a=0.6181,b=0.6136,c=0.8760nm, b = 90.17

BaBiO2.8 , Ferroelectrics Tc=370 deg.C., Rhomb. a=0.434nm, b = 89.46

Ba0.6K0.4BiO3 , - , Cubic a=0.4293nm

BaCeO3 , ? , Tetra. , a=0.6212, c=0.8804 ( c/a=1.4172 )

SrCeO3

LaErO3

KNbO3 , 435 deg.C., ( m.p.=1039 deg.C.) 0.9 (at 23 deg.C.) 30 (at 250 deg.C.)

Orthorhombic,Simple perovskite structure , LaAlO3-type compounds , Sintering difficult ?

Rhomb. => (-10 deg.C.) => Ortho. => (225 deg.C.) => Tetra. => (435 deg.C.) => Cubic

a=0.5697 , b=0.3971 , c=0.5720nm , =>K33=0.66 ( on single cristal )

NaNbO3 , 640 deg.C., ( m.p.=1412 deg.C.jOrtho.iAnti-ferroelectrics at R.T.jSimple perovskite structure

Monoclinic => (-200 deg.C. => Orhorhombic => (354 deg.C.) => Psudo-cubic => (562 deg.C.) => Tetra.=>(640 deg.C.)=> Cubic

a=0.5568, b=0.5505, c=1.5518nm

(Na0.5K0.5)NbO3 , about 420 deg.C., 33mC/cm2 , Kp=0.45? Ortho.(at R.T.) => (200 deg.C.) => Tetra. =>(420 deg.C.)=>Cubic

BaNbO3 , perovskite structure

SrNbO3 , perovskite structure

Gd1/3NbO3 , perovskite structure , NaNbO3-Gd1/3NbO3 ceramics are reported.

AgNbO3 , 70 deg.C., sintering temp.=1050 deg.C.

AgTaO3 , ?

Ag (Ta0.5Nb0.5)O3

KTaO3 , -260? deg.C., (m.p.=1357 deg.C.) , Simple perovskite structure , Quantum paraelectrics,

Not ferroelectrics, a=0.39885nm

(Li0.85Ca0.15)(Ta0.85Ti0.15)O3 (0.85LiTaO3-0.15CaTiO3) , 456 deg.C. , Kp=0.11

NaTaO3 , 630 deg.C., (m.p.=?) , Ortho. , Ferroelectrics at under at 480 deg.C., Simple perovskite structure,

a=0.54941, b=0.77508, c=0.55130nm <> Ortho.=>(550 deg.C.) => Tetra.=>(630 deg.C.)=>Cubic

(K0.5Na0.5)TaO3, -200 deg.C. , Ferroelectrics at below at -200 deg.C.

K(Ta0.55Nb0.45)O3 , KTN) , 52 deg.C. , k33=about 0.7, K31=about 0.4, (Single crystal),

Tc is 300 deg.C. or more at K(Ta0.2Nb0.8)O3 compounds.

(Bi0.5Ag0.5)NbO3 , ? , Cubic? a=0.3889nm, Attention, to prepare the compound, it is need high pressure.

0.84(Bi0.5Na0.5)TiO3-0.16(Bi0.5K0.5)TiO3 (BNT-BKT, BNKT) , Kp=0.314, BNT(Rhomb.)-BKT(Tetra.)

There is M.P.B."Phase Diagrams for Creamists" Fig. 10164 "System K0.5Bi0.5TiO3-Na0.5Bi0.5TiO3"

(Bi0.5Na0.5)0.94Ba0.06TiO3 , BNBT-6) , 288 deg.C., K33=0.55, Kp=0.3 ,

Ferroelectrics => Anti-Ferroelectrics or above at 100 deg.C. d33=125x10-12C/N

0.97(Bi0.5Na0.5)TiO3-0.03NaNbO3 , BNTN-3) , 300 deg.C., 32.6mC/cm2 , K33=0.43 , Kp=0.1 or more. ,

Relaxor ferroelectrics, Ec=5kV/mm , d33=71x10-12C/N

(Bi0.51Na0.49)(Sc0.02Ti0.98)O3 (BNST-2) , K33=0.42 , d33=71x10-12C/N

0.995(Bi0.5Na0.5)TiO3-0.005BiFeO3 , BNTF-0.5) , K33=0.46

(Bi0.45Na0.42Ba0.13)(Ti0.97Fe0.03)O3 (BNBTF (84/13/3)) , K33=0.51

(Bi0.5Na0.5)0.945Ba0.055TiO3 (BNBT-5.5, Single crystal) , d33=650x10-12C/N

(Bi0.5Na0.5)0.945Ba0.055TiO3 (BNBT-5.5, Ceramics fabricated by TGG method) , d33=490x10-12C/N

LaAlO3 , ? , Rhomb. , (m.p. = 2383 ), LaAlO3-ype compounds , a=0.5364nm , c=1.311nm

LaAlO3-SrTiO3 , Sintering temp.=1340 deg.C.or more.

NdAlO3

SmAlO3

LaGaO3 , ? , Monoclinic, GdFeO3-type, a=0.3894, b=0.3888nm

PrGaO3

LaScO3

DyScO3

LaInO3

LaLuO3

LaNiO3 , ? , Rhomb. , LaAlO3-type compounds, a=0.5395nm, a=60.8

La2/3TiO3 , ? , Orthohombic a=0.559, b=0.5601,c=0.7906nm

LaVO3 , ? , Tetragonal , a=0.5535, c=0.7830nm (c/a=1.4146)

PbVO3 , ? , < for refference > PbTiO3-type, Tetragonal , a=0.380, c=0.467nm ( c/a=1.229 )

PbVO3 need to prepare high pressure.

LaCrO3 , - , Large conductivity, Sintering of this compound is difficult.

La(Zn0.5Ti0.5)O3

La(Mg0.5Ti0.5)O3

La(Mn0.5Ti0.5)O3

La(Mn0.5Zr0.5)O3

BiFeO3 , 850 deg.C., Ferroelectrics , Rhombo. a=0.3965nm?, a = 89.24? , a=0.5616nm , a = 59.35

LaFeO3 , ? , Monoclinic , a=0.3930, b=0.3934nm GdFeO3-type

CaFeO3 , ? , Tetragonal , a=0.5326 , c=0.7579nm , (c/a=1.4230)

BiCrO3 , ? , Triclinic, a=0.390, b=0.387, c=0.390nm

BiMnO3 , ? , Triclinic, a=0.393, b=0.398, c=0.393nm

YMnO3, 641 deg.C., Ferroelectrics and Anti-ferromagnetics (Tn=-199 deg.C) , Not perovskite structure

RMnO3 , about 627 deg.C., (R=Sc,Y, In, Ho, Er, Tm, Yb, Lu)

Ferroelectrics and Anti-ferromagnetics (Tn=about -170 deg.C) , Not perovskite structure

RMnO3, ? , (R=La,Ce,Pr,Nd,Sm,Eu, Gd, Tb, Dy)

Ferroelectrics? and Anti-ferromagnetics? , Perovskite structure

BiScO3 , 480 deg.C., Rhomb., No PDF cards

BiGaO3 , ? , Rhomb., No PDF cards

BiInO3, ? , No PDF cards

BiDyO3 , - , Cubic , a=0.552nm

BiErO3 , - , Cubic a=0.5396nm

BiEuO3 , - , Cubic a=0.5483nm

BiGdO3 , - , Cubic a=0.5462nm

BiHoO3 , - , Cubic a=0.5431nm

BiSmO3 , - , Cubic a=0.5536nm

BiYO3 , - , Cubic a=0.5428nm

BiAlO3 , ? , Tetragonal , a=0.761, c=0.794nm , (c/a=1.043 )

Bi(Zn0.5Ti0.5)O3 , /// 40Bi(Zn0.5Ti0.5)O3-60SrTiO3 = (2 compounds mixture, unpublished )

Bi(Mg0.5Ti0.5)O3 , 326 deg.C.390-400? deg.C., Rhomb.? /// 70Bi(Mg0.5,Ti0.5)O3-30BaTiO3 = ( Simple perovskite, Cubic , unpublished )

Bi(Ni0.5Ti0.5)O3 , 225 deg.C., monoclinic or psudo cubic, a=0.3915, b=0.3920 nm

PZN=140 deg.C (MPB 95PZN-5PT), PMN=10 deg.C (MPB 65PMN-35PT), PNN=-150 deg.C (MPB 65PNN-35PT)

Bi(Fe0.5Ti0.5)O3

Bi(Fe0.5Ta0.5)O3

Bi(Mn0.5Ti0.5)O3

Bi(Mg0.5Zr0.5)O3 , 500?deg.C.

Bi(Zn0.5Zr0.5)O3

Bi(Mn0.5Zri0.5)O3

Bi(Ni0.5Zr0.5)O3 , ?

(La1-xBix)(Mg0.5Ti0.5)O3 , ?

Bi(Mg2/3Nb1/3)O3 , 20 ? deg.C.

Bi(Ni2/3Nb1/3)O3 , ?

Bi(Zn1/3Nb2/3)O3 , 200-300? deg.C.

Ba(Na1/2Re1/2)O3 , ? , a=0.4148 nm

Ba(Ni1/2W1/2)O3 , ? , a=0.4033 nm

Ba(Mg1/3Ta2/3)O3 , ? , a=0.4089nm, a=90 deg. 21'

Ba(Zn1/3Ta2/3)O3

Tl(Co0.5Ti0.5)O3

Tl(Co0.5Zr0.5)O3

Ce(Mn0.5Ti0.5)O3

Ce(Mn0.5Zr0.5)O3

Ca(Al1/2Nb1/2)O3

Ca(Al1/2Ta1/2)O3

Ca(Li1/2Re1/2)O3 , ? , a=0.3915nm

Sr(Fe1/2Ta1/2)O3 , ? , a=0.396 nm, c=0.3981 nm, ( c/a=1.0053 )

Sr(La1/2Ta1/2)O3

Sr(Li1/4Nb3/4)O3 , Stable complex perovskite compound

Ba(Li1/4Nb3/4)O3 , Stable complex perovskite compound?

Ba(Li1/4Nb3/4)O3-PbTiO3 Sintering temp.=1100-1350 deg.C.

Pb(Li1/4Nb3/4)O3 , Stable complex perovskite compound? <for refference >

Ca(Li1/4Nb3/4)O3 , Stable complex perovskite compound?

Sr(Fe2/3W1/3)O3 , ? , a=0.3939 nm, c=0.3953 nm, ( c/a=1.003 )

Ba2BiNbO6 , 360 deg.C., Ferroelectrics , Rhomb. , a=0.4315nm, 90.18

Ba2BiTaO6 , 400 deg.C., Ferroelectrics , Rhomb. , a=0.4284nm, 90.13

Ba2BiNbO6 , 320 deg.C., Ferroelectrics , Monoclinic , a=c=0.435nm,b=0.4311, 90.32

Ba3Bi2WO9 , 450 deg.C., Ferroelectrics , Rhomb. , a=0.4348nm, 90.20

Ba3Bi2MoO9 , 500 deg.C., Ferroelectrics , Monoclinic , a=c=0.4360nm,b=0.4321nm, b=90.30

< Ilmenite Structure >

LiNbO3 , 1210 deg.C. 10 ( ferro. => para.) (m.p.= 1253 deg.C.) 70(at R.T), Triclinic ,

Psudo-Ilmenite structure , Not perovskite structure. , (PDF card , ahex=5.1494 , chex=13.8620)

(Na0.86Li0.14)NbO3 , 400 deg.C., 15? mC/cm

Monoclinic => 20 deg.C. => Tetra. => 400 deg.C. => Psudo-Cubic , Kp=0.23 or more.

(Na0.5Li0.5)NbO3 , Kp=0.31, K33=0.31

(Na0.08Li0.92)NbO3 , Kp=0.4

LiTaO3 , 665 deg.C. 5 ferroelectric =>paraelectric )(m.p.1650 deg.C.) , 50( at R.T) , Triclinic

Psudo-Ilmenite structure , Not perovskite structure, ahex=0.515428 , chex=1.378351nm

HSbO3 , Cubic, Ilmenite structure ? (Im3)

LiSbO3 , Orth , a=0.490,b=0.8489, c=0.5181nm PDF No.43-128

NaSbO3 Rhomb., a=0.52993, c=1.54184nm , Ilmenite structure, FeTiO3-type compound, PDF No.42-223

KSbO3 , Cubic, No PDF cards, Psudo-Ilmenite structure

AgSbO3 , Pyrochlore structure?

LiBiO3 , Is there ?

NaBiO3 , a=0.55672, c=1.5989nm, Ilmenite structure

AgBiO3 , a=0.5641, c=1.6118nm, Ilmenite structure

< Tungsten-Bronze-type Oxides >

PbNb2O6 ( for refference) , 570 deg.C., Tungsten-bronze-type oxides, Kp=0.07, K33=0.38

Large anisotropic piezoelectricity

Ba4Na2Nb10O30 (BNN,banana) , 70 deg.C., 0.4C/m2 , Tungsten-bronze-type complex oxides

Ba2NaNb5O15 = NaNbO3+BaNb2O6? , =>Ferroelastic phase transition about at 300 deg.C.

Ba2NaTa5O15 (BNT)

Ba2KNb5O15 , Tungsten-bronze-type complex oxides,

Sr2KNb5O15 , Tungsten-bronze-type complex oxides,

Sr2NaNb5O15 , (SNN) , 270 deg.C., Tungsten-bronze-type complex oxides,

=>abnormal dielectric property about 200 deg.C.

K0.8Na0.2Ba2Nb5O15 , 420 deg.C., Dielectric const.=500,000? at 420??? deg.C.

(Ba1-xSrx)2NaNb5O15 (BSNN), (Ba0.4Sr0.6)2NaNb5O15 => Kt=0.148

Sr2-xCaxNaNb5O15 , SCNN) , 270 deg.C., Tungsten-bronze-type complex oxides, d33=270pC/N

K3Li2Nb5O15 (KLN) , 405 deg.C., Tungsten-bronze-type complex oxides , Tetragonal

K2BiNb5O15 (KBN) , 350 deg.C., Tungsten-bronze-type complex oxides, Ortho.

(Sr1-xBax)Nb2O6 (SBN) , Tungsten-bronze-type complex oxides

(Sr0.3Ba0.7)Nb2O6 , 180 deg.C., Sintering temp.=1200-1450 , 6.4mC/cm2

Ba5SmTi3Nb7O30 , 263 deg.C.

Ba5SmTi2ZrNb7O30 , 274 deg.C.

Ba5SmTiZr2Nb7O30 , 78 deg.C.

Ba5SmZr3Nb7O30 , -15 deg.C.

< A2B2O7 Perovskite Slab Sturcture >

Sr2Nb2O7 (SNO) , 1342 deg.C., A2B2O7 perovskite slab sturcture

Sr2Ta2O7 (STO) , -107 deg.C., Paraelectrics at R.T , A2B2O7 , perovskite slab sturcture

Sr2(Nb1-xTax)2O7 (SNTO) , 1342 deg.C.<=>(-107 deg.C.) (depending on composition) , A2B2O7 perovskite slab sturcture

La2Ti2O7 (LT?) , 1500 deg.C., A2B2O7 perovskite slab sturcture

< Layer-Structured Oxides >

AnNbn+3mO3n+3m [(ANbO3)n(NbO)3m] A=Ba,Sr,Ca,Pb...

Ba2Nb5O9 , n/m=2/1 , a=0.4172 nm , Sintering temp.=1300 deg.C.

BaNb4O6 , n/m=1/1 , a=0.4182 nm , Sintering temp.=1300 deg.C.

BaNb7O9 , n/m=1/2 , a=0.4195 nm , Sintering temp.=1300 deg.C.

Sr2Nb5O9 , n/m=2/1 , a=0.4141 nm , Sintering temp.=1400 deg.C.

Sr2Nb8O12 , n/m=2/2 , a=0.4166 nm , Sintering temp.=1400 deg.C.

< BLSF, Bismuth Layer-Structured Ferroelectrics >

For refference > In the case of BLSF, Tc of the compounds decrease with increasing ionic radius

of A-site alkaline cation generally. Tf is tolerance factor on perovskite structure,

Refference> Subbarao; J.Am.Ceram.Soc.,45, p166 (1962)

Bi3TiNbO9 , (BiBi2TiNbO9) , 930 deg.C., Tf=0.87 , (BLSO, Bismuth Layer-Structured Oxides)

Bi3TiTaO9 , (BiBi2TiTaO9) , ---- , 0.87 , Bismuth layer-structured oxides

CaBi2Nb2O9 , ---- , 0.81 , Bismuth layer-structured oxides

CaBi2Ta2O9 , ---- , 0.81 , Bismuth layer-structured oxides

SrBi2Nb2O9@(SBiN, SBN) (m=2) , 440 deg.C. (420? deg.C.) , 0.86 , BLSF , d33=10x10-12C/N

SrBi2Ta2O9@(SBTa, SBT) (m=2) , 335deg.C. , 310? deg.C.) , 0.86 , Sintering temp.=1300 , BLSF , d33=23x10-12C/N

BaBi2Nb2O9 (BaBiNb) (m=2) , ? , 0.93 , BLSF

BaBi2Ta2O9 (BaBiTa) (m=2) , 200 deg.C., 0.93 , BLSF

For refference> PbBi2Nb2O9 (PbBiNb) (m=2) , ? , 0.89 , BLSF

For refference> PbBi2Ta2O9 (PbBiTa) , (m=2) , ? , 0.89 , BLSF

Bi4Ti3O12 (m=3) (BIT) , 680 deg.C.i675? deg.C.) , 0.87 , BLSF, d33=20x10-12C/N,

(On single crystal, a-axis direction 2Pr= 100ƒC/cm2), Ceramics doped W => 2Pr=41ƒC/cm2

(Bi,La)4Ti3O12 (m=3) (BLT)

CaBi4Ti4O15 (CBT) = CaTiO3+Bi4Ti3O12 ? , (m=4) , 790 deg.C., 0.85 , BLSF

SrBi4Ti4O15 (SBT) = SrTiO3+Bi4Ti3O12 ? , (m=4) , 530 deg.C.(540? deg.C.) , 0.86

Kp=0.038, Kt=0.22, d33=15x10-12C/N , Qm=7200 , BLSF

BaBi4Ti4O15 (BaBiTi) = BaTiO3+Bi4Ti3O12 ? , (m=4) , 395 deg.C., 0.89 , d33=12x10-12C/N , BLSF

For refference> PbBi4Ti4O15 (PbBiTi) = PbTiO3+Bi4Ti3O12 ? , (m=4) ,? , 0.87 , BLSF

Bi5Ti3GaO15 (BiTiGa?) , ? , 0.87

Na0.5Bi4.5Ti4O15 (NBiTi?) = Na0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=4) , 655 deg.C., 0.86 , Kp=0.021, Kt=0.15 . BLSF

K0.5Bi4.5Ti4O15 (KBTi?) = K0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=4) 550 deg.C., 0.88, d33=10x10-12C/N, Qm=4200, BLSF

Ca2Bi4Ti5O18 (C2BT) = 2CaTiO3+Bi4Ti3O12 ? (m=5)

Sr2Bi4Ti5O18 (S2BT) = 2SrTiO3+Bi4Ti3O12 ? (m=5) , 285 deg.C., 0.86, d33=25x10-12C/N

Ba2Bi4Ti5O18 (B2BT) = 2BaTiO3+Bi4Ti3O12 ? (m=5) , 325 deg.C.(410? deg.C.) , 0.87

For refference Pb2Bi4Ti5O18 (P2BT) = 2PbTiO3+Bi4Ti3O12 ? , (m=5) , ?

ThBi2Ti2O9 , (m=2) , ? , 0.82

For refference> PbDy2Nb2O9 , (m=2) , ? , 0.89

For refference> PbBi4Zr4O15 , (m=4) , ? , 0.83

For refference> CdBi4Ti4O15 = CdTiO3+Bi4Ti3O12 ? , (m=4) , ? , 0.85

Li0.5Bi4.5Ti4O15 = Li0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=4) , ? , 0.84

Rb0.5Bi4.5Ti4O15 = Rb0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=4) , ? , 0.89

Cu0.5Bi4.5Ti4O15 = Cu0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=4) , ? , 0.86

Tl0.5Bi4.5Ti4O15 = Tl0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=4) , ? , 0.89

Ba2Bi4Ti5O18 (B2BT) = 2BaTiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.96

LiBi5Ti5O18 = CaTiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.83

NaBi5Ti5O18 = 2Na0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.85

KBi5Ti5O18 = 2K0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.89

RbBi5Ti5O18 = 2Rb0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.89

AgBi5Ti5O18 = 2Ag0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.88

TlBi5Ti5O18 = 2Tl0.5Bi0.5TiO3+Bi4Ti3O12 ? , (m=5) , ? , 0.89

SrBi2(Nb,Ta)2O9@(SBT-SBN, SBTN) , BLSF

(Sr1-xBax)Bi2Ta2O9 (SBTa-BaBTa) , BLSF

SrBi2(V,Nb)2O9@(SBV-SBN, SBVN) , 456 deg.C., 8mC/cm2 , Sintering temp.=1150 deg.C., BLSF

(Sr0.2Ca0.8)1-xNd2x/3Bi2Ta2O9 , 600-deg.C. , Kt=0.086 , Qm(t) =26800

Sintering temp.=1190-1250 dedg.C. , BLSF

Bi3TiTaO9 (BTT) (m=2) , 110 deg.C., BLSF

Bi2WO6 (BWO) (m=1) , BLSF

Na0.5Bi2.5Ta2O9 (NBT) , BLSF

K0.5Bi2.5Ta2O9 (KBT) , BLSF

Li0.5Bi2.5Ta2O9 (LBT) ? , BLSF

Na0.5Bi2.5Nb2O9 (NNT) , BLSF

K0.5Bi2.5Nb2O9 (NBT) , BLSF

Li0.5Bi2.5Nb2O9 (NBT) ? , BLSF

Bi7Ti4NbO21 (BTN) , 855 deg.C., K33=0.1 , BLSF?

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3. Representative refferencies related lead-free piezoceramics.

<(Bi0.5Na0.5)TiO3-based >

Bao et al, J.European Ceram.Soc.(2002) p2115.

Takenaka et al., Jpn.J.Appl.Phys. (1991) p2236.

Sakata et al., Ferroelectrics (1974) p.347.

Nagata et al., Jpn.J.Appl.Phys.(1998) p.5311.

Nagata et al., Jpn.J.Appl.Phys. (1997) p.6055.

Herabut et al., J.Am.Ceram. Soc.,(1997) p.2954.

< Bi(Ni,Ti)-based >

Okuda et al., Jpn.J.Appl.Phys. (1994) p5356. (Bi(Ni,Ti)O3-PT-BT)

E.Alberta et al., Ferroelectrics Letters,Vol.25(1999) p45. ( Bi(Ni,Ti)O3-PT )

< Niobates >

Kakimoto et al., Jpn.J.Appl.Phys.(2003) p.----- (KNbO3)

A.Kania et al, Ferroelectrics,Vol 52 (1984) p265. (AgNbO3)

< Tungsten-bronze-type Oxides >

Coming soon.

< Bi-layered Oxides >

Matsuda et al., Appl.Phys.Lett., Vol.85, No.7 (2004), p1220. (Bi4Ti3O12-based Film)

Maiwa et.al., Appl.Phys.Lett.,Vol.82, No.11 (2003), p1760. (Bi4Ti3O12-based Film)

Sugaya et al., J.Ceram.Soc.Jpn., (2002) p1032. ((Sr, Ca)Bi2Ta2O9)

Takenaka, J.Ceram.Soc.Jpn., vol.110 (2002) p215. (Bi4Ti3O12)

M.D.Maeder et al., J.Mater.Res.,Vol.17 (2002) p1376. (SrBi4Ti4O15)

M.V.Gelfuso, J.Am.Ceram. Soc.,(1999) p.2368. (SrBi4Ti4O15)

E.C.Subbarao, J.Am.Ceram. Soc.,(1962) p.166. (Bi-layer sompounds: Review )

Noguchi et al., J.Ceram.Soc.Jpn., 110 (2002) p999. (SrBi2Ta2O9)