Synopsis

R.V.
College Of Engineering, Bangalore-560059

(Autonomous Institution Affiliated to VTU, Belgaum)
Preparation and Characterisation of Doped

Polyvinylidene Flouride Thin Films
Prepared By
Baijayanti Ghosh 1RV13HCE03
Under the Guidance of Under the Co Guidance of

Dr. R Suresh G. Shireesha
Professor and HOD , Assistant Professor,
Chemical Engineering Department, Department of Physics,
R.V. College of Engineering R.V. College of Engineering
Contents
Smart Materials And Piezoelectricity
Smart materials are specially designed materials that show a significant
change in their property when subjected to electrical, thermal, chemical,
optical or magnetic stimulus.
Of these the most interesting and investigated are the piezoelectric
materials.
These materials produce a voltage when stress is applied. Conversely a
voltage applied across the sample will produce stress within the sample.
Comparison of piezoelectric materials
Parameter PVDF PZT Quartz Units
(Polymer) (Ceramic) (Crystal)
Piezostrain constant (g33) 240 11 50 V/m
Electric Field Produced / Stress Applied N/m 2
Young's Modulus (Stress/ Strain ) 8-9 70-110 70-90 GPa
Density 1180 7800 2700 Kg/m3
Brittleness Low Very High High -
Surface Resistivity(resistance to leakage 1013 1010 1013 ohm
current along the surface )
Baijayanti Ghosh, M Tech, Dept of Chemical Engineering, RVCE, 21 st November 2014. Slide 1 of 20
Polyvinylidene Fluoride
Polyvinylidene fluoride (PVDF) is a highly non-reactive and pure
thermoplastic fluoropolymer .
When doped with the right dopants can exhibit piezoelectric,
magnetorestrictive and thermoelectric molecules.
H F
C Xn
H F
PVDF is typically a semicrystalline polymer that is approximately 50%

amorphous.
The most interesting and investigated properties of PVDF are its
polymorphism and piezoelectricity.
Stable Polymorphism Of PVDF
Alpha Phase (TGTG) Beta Phase(TT)
Gamma Phase (TTGTTG)
Piezoelectricity in Phase pvdf
Direction of
polymerisation
Direction of field opposite

to polymerisation
Direction of field is parallel to

polymerisation
Phase Transitions In PVDF
Applications of PVDF
The Approximate Distribution of Papers Published on Various Applications
Key literature survey
Author Aim of Work Conclusions
Daniel M. Studied the methods of phase films were formed when a solution of
Esterly preparation of PVDF film and PVDF powder in Dimethyl formamide at 60C
(2002) their effects on structural and was subjected to spin coating
mechanical properties
R. Danz et Studied the structural and electric phase concentration increased with dye
al. (2002) and magnetic properties of concentration
PVDF doped with different Ferroelectric effect increased with dye
concentrations of crystal violet concentration
dye(hexamethyl pararosaniline
chloride)
A. G. Emslie Developed a model to derive a Film thickness was inversely proportional to
(2009) relation between thickness of the rpm to the power of 2/3
film, properties of the solution & Film thickness was inversely proportional to
speed square root of time
Nithi Atthi et Studied the optimization of A dispensing time of 13 seconds at 100 rpm
al. (2010) condition for spin coating of the & acceleration at a speed of 1000 rpm at 10
photoresist film on rectangular seconds was found to give uniform thickness.
substrate by Taguchi design of an
experiment
Key literature survey
Author Aim of Work Conclusions
Dhakras et al. Studied the effect of addition of Addition of the hydrated salt (NC) was found to
(2012) a hydrated salt, nickel chloride enhance the polar phase by about 30%.
hexahydrate (NiCl2.6H2O), on
the phase formation of PVDF
fibers.
M. Obula Studied the Structural, Transition metal ions doped in PVDF matrix
Reddy et al. Dielectric, Optical and Magnetic enhanced the magnetic and optical properties of
(2013) Properties of Ti3+, Cr3+, and Fe3+ PVDF thin Films
doped PVDF thin films
Gaps in Previous Study

1. PVDF thin film doped with MnCl2,FeCl3 Ti3+ ions and crystal violet dye has been studied and
yielded favourable results however a combination of these has not been studied .
2. The effect of Nickel on PVDF fibres have been studied but not PVDF thin films.
3. Modelling of spin coating of PVDF thin films is yet to be documented.
4. Optimisation of spin coating of PVDF thin films has never been documented.
5. The application of the fore mentioned doped PVDF thin films has never been carried out.
Spin coating
The deposition process involves the dispense of an

excessive amount of fluid onto a stationary or
slowly spinning substrate.
In the spin up stage, the substrate is accelerated to

the final spin speed. A wave front forms and flows
to the substrate edge by centrifugal force leaving
a substrate with uniform thickness.
The spin off stage is the spin coating stage

where the excess solvent is flung off the
substrate surface as it rotates at speeds between
800 and 1000 RPMs
Modeling Of Spin Coating Process
At the start of the spin off stage there is a balance

between viscous and centrifugal force
= absolute viscosity
d 2v
2 2 r = fluid density
dz v = velocity in the direction of r
Integrating with respective Z and using suitable boundary

condition of zero shears at the free surface i.e. /z = 0

h
q vz dz 2 rh 2 / 3
0
Where q is the flow per unit circumference
Using the continuity with polar co ordinates

ho Where ho and ht are the initial and film thickness
ht
1 4h 2
0 2 t / 3
1/ 2
ht 1 / & ht 1 / t 0.5
Issues in Spin Coating Rectangular Substrates
Edge Bead Formation
Caused by physical properties, unfavorable spin recipe
and early drying at periphery
Avoided by
Beveling the edges of the substrate
Spraying the edge with a solvent spray during spinning
Geometrical Effects
Caused due to increased friction with air at the
periphery in a non circular substrate
Avoided by
Air barrier or a cover
Bernoulli Effect
This is the result of the leading edge of the substrate in
addition to the edge bead creating an airfoil, in which the air
streamline separates as the substrate pins
Avoided by
Placing the substrate on a recessed chuck
Baijayanti Ghosh, M Tech, Dept of Chemical Engineering, RVCE, 21 st November 2014. Slide 1 1 of 20
Experimental Procedure
Stage-1 PVDF Film Preparation
10 ml DMF + 100 ml beaker + Hot Plate

2 gm PVDF Solution Preparation and heating to 60C
Dispensing
Spin Coater
Spinning at 100 RPM
Spin Coater
Excess
Spinning at 500 RPM
Solvent
Drier
Excess
Annealing at 60C for 4 hours
Solvent
Peeling of the thin film
Stage-2 PVDF Film Preparation with dopants
4 ml DMF + Dopants 6 ml DMF + 4 gm PVDF
100 ml beaker+ Ultrasonicator 100 ml beaker

Dopant Solution Preparation PVDF Solution Preparation
100 ml beaker+ Ultrasonicator

Solution preparation at 60C
Spin Coater + Dryer

Spin Coating and drying
Dopant Concentration
PVDF- X gm
TiO2 + MnCl2 Crystal Violet Dye + FeCl3 Nickel Chloride hexahydrate
10,15,20 wt. % of x 20,30,40 wt. % of x , NiCl2.6H2O
X= y TiO2+ 4 y MnCl2 X=yFeCl3+ 10y Violet Dye 10,15,20 wt. % of x ,
Stage-3 Study of optimization conditions for spin coating
Design Of Experiment
Keeping all properties of PVDF Solution constant
Varying Dispensing Parameters Varying spinning speed Varying acceleration
Vary RPM Vary time Vary RPM Vary RPM

400-600 13-16 s 500-800 800-1000
Measurement Plan Fitting Model for Spinning Stage

ho
ht
1 7 3
1 4h02 2 t / 3
1/ 2
= absolute viscosity
5
= fluid density
2 4 ho = initial height
6
ht = final height
Material Analysis
Film Analysis
Structural Mechanical Thermal
Differential
Scanning electron Izod Impact Testing
Scanning
Microscopy
Calorimeter
Fourier Transform Tensile Strength
Thermo gravimetric
Infrared Spectrometry Analysis
Flexural Strength
X Ray Diffraction Heat deflection
Weathering temperature
Material Analysis
Film Analysis
Electrical Optical Physical Magnetic
Dielectric constant Spectrophotometer Density Hysteresis

(Energy gap analysis) loop study
Hardness D
Surface Resistivity Raman's
Spectrophotometer
Film
Gloss Thickness
Volume
Resistivity
Expected Results
Comparison of external morphology of doped PVDF (At different concentrations) and pure
PVDF film to corroborate with XRD and FTIR results.
The XRD is to be measured as a function of concentration.
The DSC, TGA is to be measured as a function of concentration.
The mechanical strength is yet to be documented as a function of dopant
concentration however commercially available thin films of pure PVDF have a tensile
strength between 60-160 MPA.
The electrical resistance of film is expected to decrease with increase in dopant
concentration due to its semiconducting property.
The optical absorbance is to be measured as a function of dopant concentration.
Hardness and density of film is yet to be documented as a function of concentration of
dopant. Film thickness is expected to be in 100-150 micron range.
The effect of dopant concentration is top be found on hysteresis loop.
Experimental Procedure Carried out
Fixing the concentration
Sl No Concentration Film Thickness
1. 1 gm of PVDF+10 ml of DMF < 10 ppm
2. 2 gm of PVDF + 10 ml of DMF 20 ppm
3. 3 gm of PVDF + 10 ml of DMF 50-60 ppm
4. Maximum amount that can dissolve in 10 ml of DMF 80-100 ppm
Heating of the solution to 60C

Sl No Heating Time Solution Nature
1. Heating on plate directly to 60C in 5 minutes Yellow & degraded
2. Heating on plate directly to 60C in 10 minutes Light Yellow & degraded
3. Heating on plate ramped 10 C every 5 minutes Colourless
Project Timeline
Project till now
Process June July Aug Sept Oct Nov
1.) Literature Survey
2.) Material and Glassware requisition
3.) Preparation of Facilities for
experiment
4.) Initiation of Experiment
Plan forward
Process Dec Jan Feb Mar Apr May June

1.) Optimisation Study of Thin Film Spin coating
2.) Preparation of doped PVDF Films
3.) Characterisation of films
4.)Testing & Application In Sensors
5.) Record Writing/ Paper Writing
Baijayanti Ghosh, M Tech, Dept of Chemical Engineering, RVCE, 21 st November 2014. Slide 1 9 of 20
Plan Forward
Strain Sensor Circuit
To Oscilloscope
Sensor Construction
All dimensions in mm
Thank You

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R.V.

College Of Engineering, Bangalore-560059

Preparation and Characterisation of Doped

Under the Guidance of Under the Co Guidance of

PVDF is typically a semicrystalline polymer that is approximately 50%

Gamma Phase (TTGTTG)

Direction of field opposite

Direction of field is parallel to

Gaps in Previous Study

The deposition process involves the dispense of an

In the spin up stage, the substrate is accelerated to

The spin off stage is the spin coating stage

At the start of the spin off stage there is a balance

Integrating with respective Z and using suitable boundary

Using the continuity with polar co ordinates

10 ml DMF + 100 ml beaker + Hot Plate

4 ml DMF + Dopants 6 ml DMF + 4 gm PVDF

100 ml beaker+ Ultrasonicator 100 ml beaker

100 ml beaker+ Ultrasonicator

Spin Coater + Dryer

Keeping all properties of PVDF Solution constant

Varying Dispensing Parameters Varying spinning speed Varying acceleration

Vary RPM Vary time Vary RPM Vary RPM

Measurement Plan Fitting Model for Spinning Stage

Structural Mechanical Thermal

Electrical Optical Physical Magnetic

Dielectric constant Spectrophotometer Density Hysteresis

Heating of the solution to 60C

Process Dec Jan Feb Mar Apr May June

4.)Testing & Application In Sensors

5.) Record Writing/ Paper Writing

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