H.K.E.

SOCIETY’S

POOJYA DODDAPPA APPA COLLEGE OF ENGINEERING, GULBARGA

(An Autonomous Institution, Affiliated to VTU Belgaum, & Approved by AICTE)

INTERNSHIP

ON

“LEAD-FREE PIEZO-MATERIAL’’

Under the Guidance By

DR.P.K.PANDA

Submitted By

VIKAS (3PD16CC035)

Bachelor of Engineering In Ceramic and Cement Technology

Table 1. History of piezoelectric materials
1978 Engineered (connectivity designed) FE composites developed

1980 Electrostrictive relaxor PMN devices developed, Pat. No. 5 345 139

1981 Sol–gel techniques developed for the preparation of FE films

1983 Photostrictive effects reported in PZT and PLZT

1991 Moonie piezo flextensional devices developed, Pat.No. 4 999 819

1992 RAINBOW piezo bending actuators developed, Pat.No. 5 471 721

1993 Integration of FE films to silicon technology, Pat. No. 5 038 323

1997 Relaxor single-crystal materials developed for piezo transducers

1998 Development of cymbal actuator, US. Pat. No. 5 729 077

2002 Composite piezoelectric patch actuator.

 INTRODUCTION

The word Piezoelectricity means electricity resulting from

Pressure & latent heat. Piezoelectricity it is the ability of
certain materials to generates an AC (Alternating Current)
voltage when subjected to mechanical stress or vibration or to
vibrate when subjected to an AC voltage or both the most
common Piezoelectric materials is Quartz. Which is
accumulates in certain solid materials ( such as crystals,
certain ceramic & Biological things such as DNA & various
Proteins.)

Types of Piezo-Ceramic Materials

1.Lead Zirconate Titanate ( PZT )

2.Barium Titanate ( BaTio3 )
1.Lead Zirconate Titanate (PZT)

The Piezoelectric-ceramics which are first time practically used in 1950

& which are used in wide range of industries since then. Normally PZT
have two materials.
• Ferroelctric Lead Titanate &
•Anti-Ferroelectric Lead Titanate.

Many of the devices are used in this process such aas electromechanical
transducers ability, including communication & actuators. The ‘Zr’
structure isd Rhombohedral & Ti structure is Tetragonal. The PZT has a
Perovskite type of crystalline structure. Which is represented by the
composition of Formula ABO3.
2.Barium Titanate ( BaTio3)

Barium Totanate ( BaTio3), was which inventioned on during world war-

II which are formed by various ceramic techniques & which was first
ferroelectric oxide with a perovskite structure. Normally ceramic has a
relatively high electromechanical coupling factor. The working
temperature of barium titanate is narrow , present in piezoelectric
application because Barium Titanate has low curie temperature which as
drawback of Barium Titanate . Recently which has Piezoelectric Strain
constant
( d33 = 350 PCLN & d33 = 450 PCLN )
 PIEZOELECTRICITY

Piezoelectricity was discovered in the year 1880 By Nobel Laureates Pierre and Jacques
Curie
Direct Effect: Mechanical stress leads to the generation of electric charge.
Converse Effect: An electric field leads to a strain (expansion or contraction).

Converse (motor) effect

Direction
Poling

No load Disc Disc Expanded by Contracted by

compressed stretched application of +ve application of –ve
+ve voltage -ve voltage voltage voltage
generated generated

Direct Effect Converse Effect

 Hysteresis Curve

The plot of P vs E in which the material is polarized same

direction 7 & then opposite direction is called hysteresis curve.
The ferroelectric of specimen which are initially unpolarized.
Which subjected to the electric field of the polarization P
varies with E remaining in the polarization can be reduce to
zero. Which called remanent polarization. In this power of the
material of retaining of this polarization is called retentivity of
the materials. A material is said to be spontaneously polarized
when electric field E is zero but when polarization of P is not
zero this phenomenon is called spontaneous.
Fig.1.5. A typical P-E hysteresis loop in ferroelectrics
 PROBLEM WITH LEAD?-ALTERNATIVES
In response to concerns for the environment and human health, the
European Union has introduced a legislation to ban lead from electronic
products by July 1st 2006.
Hence environment friendly lead free piezoelectric materials are being
developed to replace the PZT- based materials.
The new alternatives for lead free materials are,
• Alkaline Niobate- based perovskite
• Bismuth Titanate based layered compounds
• Bismuth Layered structured Ferroelectrics
• Tungsten bronze structure
However, no materials display more excellent piezoelectric properties than
PZT systems.
Perovskite type lead free ceramics seem to be suitable for actuator and high
power applications which require a high d33 and Curie temperature.
 PROCESS FLOW SHEET OF PZT POWDERS

Lead Precursor Zirconium precursor Titanium precursor Dopant Solution

Solution Solution Solution

Gelation, pH=8-8.5

Calcination at 750-850C

Deagglomeration

Granulation &Compaction

Sintering at 1050-1250C/ 2hrs

Poling & Characterization

 32
Symmetry point groups

21 11
Noncentrosymmetric Centrosymmetric (non piezoelectric)

20
Piezoelectric (Polarized under stress) Tungsten Bronze (PbNb2O8)

10 Pyrochlore (CdNb2O7)
Pyroelectric (Polarized upon heating)

Layered Structure (BiTi3O12)

Ferroelectric (Spontaneous & reversible polarization)

Oxygen Octahedra (ABO3)

BaTiO3 PZT PMN PLZT (Na,K)NbO3

Fig.1.3. Interrelationship of piezoelectric and subgroups on the basis of

symmetry
 Synthesis of BaTiO3
Baco3 Tio2

mixing

Calcination (1200C/h)

De-agglomeration/ Soft
ball milling

Mixing with PVA binder

Pressed to Pellets
Flow Sheet of Lead Free Piezo-Materials:

Raw Materials
Oxides & Carbonates

Mixing

Calcination

Characterization
(XRD,SEM,ParticleSize)
Characterization
Sintered 1.XRD
2.SEM
3.d33
4.K
Sintered Disc
 Advantages of Lead Free Piezo Materials

 For High temperature applications bismuth-layered compounds show

good stability of properties and hence they serve as excellent
candidates for piezoelectric sensors.
 For low temperature applications sodium potassium niobate and
bismuth sodium titanate perovskite type ceramics seems to be suitable
for actuator and high power applications.
 Though the d33 properties of Lead free systems are less compared to
PZT systems, the d33 value per specific weight of these systems are
comparable to PZT.
 Due to low density, lead free piezo materials could be suitable for
under water transducer applications
 The piezo properties of lead free single crystals should be of
comparable with polycrystalline PZT materials
APPLICATIONS OF PIEZOMATERIALS

Electrical to Mechanical Mechanical to Electrical

conversion conversion
• Valves • Phonograph cartridges
• Micropumps • Microphones
• Earthphones & speakers • Vibration sensors
• Ultrasonic cleaners • Accelerometers
• Emulsfiers • Photoflash actuators
• Sonic transducers • Gas igniters
• Fuses
Fig.1.13a. Piezometer with force head Fig.1.13b Force head with sample
 PUBLICATIONS
1. Preparation of pyrochlore free PMN powder by semi-wet chemical route. Materials Chemistry
and Physics, 93 (2005) 231-236.
P.K. Panda and B.Sahoo
2. Development of PZT powders by wet chemical method and fabrication of multilayered
stacks/actuators. Material Science and Engineering B:126 (2006) 80-85.
B.Sahoo, V.A. Jaleel and P.K.Panda
3. Dielectric,ferroelectric and piezoelectric properties of PLZT-PMN materials. Journal of
Materials Science, 42 (2007) 4270-75.
B.Sahoo and P.K.Panda
4. Effect of CeO2 concentration on dielectric, ferroelectric and piezoelectric properties of PMN-
PT (67/33) composition. Journal of Materials Sciences, 42 (2007) 4745-52.
B.Sahoo and P.K.Panda
5. Ferroelectric, dielectric and piezoelectric properties of Pb1-x Cex (Zr0.60Ti0.40)O3, 0 x 0.08.
B.Sahoo and P.K.Panda, Journal of Materials Sciences , 42 (2007) 9684-9688
6. Review: Environmental friendly lead free piezoelectric materials
P.K.Panda, Journal of Materials Science, 44(2009)5049-62.