ELECTROACTIVE POLYMERS:

Insight, Applications and Challenges

V. Sencadas, J.Gomes, S. Lanceros-Mendez Physics Department University of Minho

MIICS 2008

Summary

Electroactive Polymers Overview

PVDF Polymer

Other Smart Materials

Processing Techniques

Characterization Techniques

Applications

Partners

Introduction
Multifunctional materials:
several functionalities e.g. sensor/actuator the same material have

Smart materials:

respond to an excitation force with a significant (and reproductive) variation of a given physical property

Smart structures:

structures with increased functionality (e.g. failure detection and warning (even repairing); health monitoring; MEMS)

Electroactive Polymers:
Overview
Materials that respond, in reproducible and stable form, with a significant external variation in certain property when subjected to an external stimulus.

Stimulus

Answer

Stimuli: Mechanical Electric Thermal

Answer: Mechanical Electric

Electroactive Polymers:
Overview
Are lightweight, flexible and tough Can be obtained in the form of ultrathin films, fibers and even liquid crystals

Can be easily transformed into to the desired configuration

Why Polymers

Some of them are biocampatible.

Their physical properties can be controlled over a wide range by appropriate chemical modifications

Some have piezo-, pyro- and ferroelectric properties

Electroactive Polymers:
Overview
Piezoelectric and Pyroelectric Polymers
Dynamic response

P d ij = i j

E ,T i , j =1, 2, 3

P p= T
3 (direction of the applied electric field)

1 (direction of the mechanical force) 2 (perpendicular to the mechanical force direction)

Electroactive Polymers:
Overview

NASA Space Centre, ICASE PIEZOElectric Materials, 2001

Electroactive Polymers:
Overview
p
(mC.m-2K1)
40 30 - 40 3 60-500 200 ___

Material
PVDF P(VDF-TrFE) Nylon 11 PZT-5 BaTiO3 Quartzo

(g.cm-3)
1,76 1,9 1,1 7,75 5,7 2,86

r (1kHz)
8-13 15 20 4 700 1700 4,5

d31 (pC.N-1)
20 15 30 3 171 78 2

k
(%)
6 20 ___ 34 21 9

Materials PVDF Poly(vinylidene Fluoride)

Crystalline Region

Phase - Phase -
Amorphous Region

PVDF
Phase - Phase -
Spherulite Nucleus

PVDF Poly(vinylidene Fluoride)

Monomer

-PVDF

-PVDF

PVDF Poly(vinylidene Fluoride)

Processing conditions enable the control of the materials properties:

Morphology

Crystalline Phase
20

Mechanical Properties

Ferroelectric Behaviour

10

Q / mW

Thermal properties

-10

140C 142.5C 145C 147.5C

6.0 6.5 7.0 7.5 8.0

time / min

PVDF Poly(vinylidene Fluoride)

Crystallization kinetics: Phase and microstructure formation

80 70 60
-PVDF 150C -PVDF 155C -PVDF 160C -PVDF 165C -PVDF 160C -PVDF 165C

140C

150C

Radius / m

50 40 30 20 10 0 0 20 40 60 80 100 120

140

160

180

time / min
-PVDF

Ln(G) / m.min

-1

-1

-PVDF

-4.4

Ln(G) / m.min

-4.8

-2

-5.2

-3
-5.6

-1

160C

165C

150

155

160

165

T / C

Some Results: to phase transformation

R=3
15

R=4

12

/ MPa

R=3 R=4
9

R=5
12 3.00E-009

R=2

10 2.00E-009 8

/ MPa

V/V

Tenso V

1.00E-009

4 0.00E+000

R=1

0 0 5

Transio de fase?
10 15 20

-1.00E-009

25

F ( ) =

A ( K / K ) A + A

/%

0 0 100 200 300 400 500 600 700

/%

R=1
F() / %

80

80C

R=5

90C 60 100C 40 140C 20

0 1 2 3 4 5

Some Results: 100% phase material

PCT/IB 2006052474
80

Transmitncia / %

60
(442) (600) (510)

40

20
(840)

0 400

500

600

700

800

Nmero de onda / cm

900 -1

1000

Results
Dynamical Mechanical Behavior

7000

6000

-PVDF

0.16 0.14 0.12

-PVDF

5000

E' / MPa

80C R=5 80C R=5 140C R=5 140C R=5

80C R=5 80C R=5 140C R=5 140C R=5

4000

Tan
-60 -30 0 30 60 90 120 150

0.10 0.08

3000

2000

0.06 0.04 0.02 -50 0 50 100 150

1000

Temperature / C

Temperature / C

All samples have similar mechanical behaviour E is higher for the unoriented samples (-PVDF) A relaxation process is detected at T -35 C. This process, has been labelled or a. It is assigned to the cooperative segmental motions within the main chains of the amorphous regions Above 50C (for the stretched samples), a new relaxation process appears associated to -relaxation. Absent in amorphous PVDF.

Results

Dielectric Behavior

30

1.00

20

-PVDF
25

R=5
15

T80R5 T140R5

0.75

20

ln() / Hz

80C 90C 100C 140C

10

Tan

'

15

0.50

10 0.25

0
5 0.00 0 -100 -50 0 50 100 150

-5 0.0030

0.0033

0.0036

T / C

1/T / K

0.0039 -1

0.0042

0.0045

20

T = 80C
15

R1 R4 R5

Increase of the dielectric constant with increasing -phase content. Effect of stretching temperature in the relaxation behavior is much lower than the effect of the stretching ratio.

ln()

10

-5 0.0030 0.0033 0.0036

1/T / K

0.0039 -1

0.0042

0.0045

Phase content and orientation (mainly) play a very important role on the relaxation parameters.

Results VFT Fitting Results

80C R 1 4 5

0
s-1 1.84E-10 9.2E-11 2.77E-11

Ea
eV 0.061 0.073 0.087

TVF
K 200.40 208.90 193.92

Tg
K 226.42 239.57 228.67

m
102.10 94.03 82.65

VFT
= 0 exp
Ea k B (T TVF )

R5 T (C) 80 90 100 140

0
s-1 2.77E-11 2.2E-11 6.54E-11 9.31E-11

Ea
eV 0.087 0.085 0.071 0.070

TVF
K 193.92 195.92 201.64 199.47

Tg
K 228.67 229.84 230.99 229.11

m
82.65 85.75 95.92 99.29

Fragility parameter
m= EVTF / kTg (ln 10)(1 T0 / Tg ) 2

Results

Dielectrical vs Dynamical Mechanical

30 7000

-PVDF
25

T80R5 T140R5

6000 5000

0.45

-PVDF

T80R5 T140R5

0.15

Tan

4000

Tan

20

0.12 0.30 0.09

E / MPa

'

15

3000 2000 1000 0

10

0.15

0.06

0.03 0.00

0 -100

-50

50

100

150

-100

-50

50

100

150

T / C

T / C

20 15 10

T = 80C

The -relaxation is identified by an increase of E and a corresponding decrease of , i.e. an increase in the mechanical stiffness and a decrease in the dipole mobility The -relaxation is mainly observed in the mechanical experiments, especially in the measurements performed parallel to the draw direction.

ln()

5 0 -5 -10 -15 0.0030

R1 R4 R5
0.0033 0.0036 0.0039 -1 0.0042 0.0045

1/T / K

Results
Dielectrical vs Dynamical Mechanical
20 15 10

80C
ln()

16 12 8 4 0 -4 -8 0.0034 0.0036 0.0038 0.0040

-1

90C

ln()

5 0 -5 -10

Dielectric Mechanical - Paralel Mechanical - Perpendicular

-15 0.0030 0.0032 0.0034 0.0036 0.0038 0.0040 0.0042 0.0044 1/T / K
-1

Dielectric Mechanical - Paralel Mechanical - Perpendicular

0.0042 0.0044

1/T / K
16 12 8

100C

20 16 12

140C

ln()

4 0 -4 -8 -12 0.0032

ln()
Dielectric Mechanical - Paralel Mechanical - Perpendicular
0.0034 0.0036 0.0038 0.0040
-1

8 4 0 -4 -8 0.0032 0.0034 0.0036 0.0038 0.0040

-1

Dielectric Mechanical - Paralel Mechanical - Perpendicular

0.0042 0.0044

0.0042

0.0044

1/T / K

1/T /K

Optimization and origin of the electroactive properties

8,0x10 -2 6,0x10 -2 4,0x10 -2 2,0x10 P (C/m2) 0,0 -2 -2,0x10 -2 -4,0x10 -2 -6,0x10 -2 -8,0x10
-2

E=100MV/m; =10Hz E=130MV/m; =10Hz

0,0 -3,0x10
-3 -3

E=100MV/m; =10Hz E=130MV/m; =10Hz

-6,0x10 S -3 -9,0x10 -1,2x10 -1,5x10 -1,8x10

-2 -2 -2

-1,2x10 -6,0x10

0,0
E (V/m)

6,0x10 1,2x10

-1,2x10 -6,0x10

0,0 6,0x107 1,2x108 E (V/m)

0,0 -3,0x10
-3 -3

Field (kV/mm) 1

(Hz) 67

33 12

d33 (m/V) 23e-12

-6,0x10 s -3 -9,0x10 -1,2x10 -1,5x10 -1,8x10

-2 -2 -2 -2

E=100MV/m; =10Hz E=130MV/m; =10Hz

-2

-8,0x10 -4,0x10

0,0 4,0x10-2 8,0x10-2 2 P(C/m )

Optimization and origin of the electroactive properties

Non-poled
300nm

300nm
0.00E+00 -80 -60 -40 -20 -5.00E-06 0 20 40 60 80

-1.00E-05

-1.50E-05

-2.00E-05

-2.50E-05

-3.00E-05

-3.50E-05

-4.00E-05

-4.50E-05

-5.00E-05

Smart Materials
Other Smart Materials being developed:
Conductive Polymers (PANI, Ppy, PEDOT:PSS) Polymer-matrix (PVDF) composites
PVDF Ag nanoparticle composites PVDF-PZT composites PVDF- Carbon nanotubes/ Carbon nanofibre composites

Polymer-matrix (PVDF) Magnetoelectric composites Piezoresistive Materials

Processing Techniques

Sheet Extrusion (Thin Film)

Tricomponent Extrusion

Electrospinning / Meltspinning

Spin Coating

Inkjet Printing

PVD

Characterization Techniques

Microscopy

SPM -AFM

SEM

Optical Microscopy

Characterization Techniques
Electrical Analysis

Ferroelectric Properties

Conductivity

EFM, MFM, PFM

Dielectric Spectroscopy

Mechanical and Thermal Analysis

DSC-TGA

DMA

Stress - Strain

Applications
Key features of Piezoelectric Polymers:
Low density Multi-Shape possibilities High flexibility Ideal for wearable sensor actuator applications Low cost (processing and materials) Tunability

Applications
Vibration Monitoring
Airplane Wings Buildings and Structures

Bio Sensors
Electroactive Scaffolds Implant healt monitoring systems Physiological condition monitoring (heart rate, temperature)

Wearables
Flexible and Transparent Touchpads in clothing Flexible microphones Flexible sensor-actuators in footwear

Applications
Energy - Electronics Photovoltaic Solar Cells (EU funded project) Energy generating devices Upgraded Electronic devices Multimedia Flexible and Transparent Touchpads and Touchscreens Electrochromic effects Interactive Structures Others Applications involving an electric/mechanical stimuli resulting in an electric, mechanical, optic or thermal response

Flux sensor
Ultrasound transducer Pipe Ultrasounds Suspended particles

Flow direction

Ultrasound transducer

Sensor based on the Doppler Effect. One ultrasound transducer emits ultrasounds, at a frequency of hundreds of kHz, through the flow. The particles suspended in the liquid reflect the ultrasounds to a second transducer that will receive them.

Challenges
Optimization of the electroactive response Optimization of physical properties copolymers and blends; doping Multifunctional materials: Adding metallic nano-particles (Optical properties) Adding carbon nano-fibers and nanotubes (thermal and electrical properties) Processing in the form of film or long/short fibers Processing porous or nonporous material Processing of ultrathin films (10 100 nm)
1.4m

Application Challenges

Generation and accumulation of energy (ex. shoe/textile) Multifunctional actuation (heating, force, ) Flexible sensors (breath, heart, etc), implementation in cloths, etc Electro-active fibers Flexible tactile, temperature, form and shape sensors. Interactive, flexible displays Electro-chromic Stimulation or cell growth
~ 0.22 0.036 pC/N 800nm

Partners
National:
-Universidade do Minho -Universidade de Aveiro -Universidade do Porto - CeNTI, Centre for Nanotechnology
and Smart Materials

International:
-University of Halle (Germany)

-University of Postdam (Germany) -Montana State University (USA) -Pennsilvania state Unversity (USA) -Universidade Politcnica de Valencia (Spain) -Universidad del pas Vasco (Spain)

Industry:
- Amtrol-Alfa; - Galp (projects); Shoes; Foams (projects); -MSI; -Solvay (material)

-Universidade Federal de So Carlos (Brazil)

Acknowledgments
Bilateral cooperation programs CRUP (Brasil, Spain, Germany) Portuguese Foundation for Science and Technology (FCT), several project fundings and PhD grants COST-12 Structuring Polymers SIUPI program for up-scaling of processes Plastinet alpha program from EU

Special thanks to the Organizers

Internet webpage
http://www.arauto.uminho.pt/pessoas/lanceros/ProjectoPiezo/index.html