EIS

G.P. Chaudhari
 Areas for Using EIS
• rapid estimation of CR ( 30 min to 24 h)
• extremely low CR (<10-4 mm/year)
• Low conductivity media
• inhibitor performance
• fast evaluation of coatings
 Ideal Resistor
E
R
I
– follows Ohm’s law at all voltage and current levels
– Its resistance value is independent of frequency.
– AC current and voltage signals though a resistor are
in phase with each other.
• In reality, rarely ideal resistors but some other
complex circuit elements that do not fulfill all of
the above conditions => Impedance
• Like resistor an impedance is a measure of
resistance to the flow of current in a circuit
 Electrochemical Impedance

• apply a sinusoidal voltage

purturbation (AC potential) to a cell
and measure the current through
the cell => get impedance
• Electrochemical Impedance is
normally measured using a small
excitation signal. This is done so
that the cell's response is pseudo-
linear. In a linear (or pseudolinear)
system, the current response to a
sinusoidal potential will also be
sinusoidal at the same frequency
but shifted in phase.
 Pseudo-linear response
• Impedance analysis of linear circuits is much easier than analysis of non-
linear ones
• Electrochemical cells are non-linear, doubling the voltage does not
necessarily double the current response
• But it can be pseudo-linear if very small perturbation pulse is applied,
• 1-10mV AC
• Purturbation (excitation) v(t )  Vm sin(t )
signal
• v is potential at time t
• Vm is the amplitude
  2f
• ω is the radial frequency,
rad/s
• f is in Hz
• In linear system, response
i (t )  I m sin(t   )
signal i(t) is shifted in
phase by φ
v(t ) Vm sin(t ) sin(t )
Z   Zm
i (t ) I m sin(t   ) sin(t   )
Impedance is expressed in terms of magnitude Zm, and a phase shift φ
Impedance as a complex function
vt  Vm exp( jt )
it  I m exp( jt   )
vt
Z ( )   Z m exp( j )
it
using Eulers relationship:

Z ( )  Z m (cos   j sin  )

Z(ω) consists of a real part and an imaginary part

If we plot real Z on the abscissa and imaginary Z on the ordinate =>
Nyquist Plot
 The Nyquist Plot with impedance vector
eqvt ckt with
one time
constant

• each point on the plot is impedance at a given frequency, ω

• low frequency data are on the right (no magnitude is depicted, only range)
• impedance is a vector of length IzI and phase angle is φ(=arg Z)
 The Bode Plot
• It shows the frequency information
• IZI vs log (ω), and
• Phase angle (shift) vs log(ω)
 Fitting of EIS data
• EIS data is analyzed by fitting it to an eqv ckt model
• Common circuit elements:

Circuit V-I Impedance

Component relationship
Resistor V=IR Z=R
Capacitor V=C dV/dt Z=1/jωC
Inductor V=L di/dt Z=jωL
• resistor: impedance is independent of frequency, has no imaginary component
•With only a real impedance component, the current through a resistor
stays in phase with the voltage across the resistor.
•Capacitor: opposite to that of an inductor. i.e. it’s impedance decreases as the
frequency is raised.
•Capacitors also have only an imaginary impedance component.
The current through an capacitor is phase shifted 90 degrees with respect
to the voltage.
Inductor: impedance increases as frequency increases, have only an imaginary
impedance component.
Hence, the current through an inductor is phase-shifted -90 degrees with
 Combinations of ckt elements
• series and/or parallel
• series: Z = Z1+Z2+Z3+…

1 1 1
• parallel:  
Z Z1 Z 2
 ....
Modeling of Impedance Spectra
• assuming a circuit made of different
elements
• Find values of elements
• Relate these values to a physical
phenomena so that it reasonably
represents a corrosion process
Physical Significance of Circuit Elements

• elements in the model should have physical significance

in the electrochemistry l
• Solution Resistance~ Resistor, R  
A
– it is calculated when EIS data is fitted to a model
• Double Layer: Cdl. On a bare metal in an electrolyte ~ 20-
60 μfd/cm2 .
• Rp ~ resistor
• Coating Capacitance
• Virtual Inductor- a curve fitting ckt element
– formation of a surface layer like passive layer or fouling
– may result from errors in measurement, non-ideal potentiostat
 Types of Models
• In a physical model, each of the model's components is
postulated to come from a physical process in the
electrochemical cell
• The choice of which physical model applies to a given
cell is made from knowledge of the cell's physical
characteristics
• EIS analysts can use the shape of a cell's EIS spectrum
to help choose a model for that cell
• Models can also be partially or completely empirical. The
circuit components in this type of model are not assigned
to physical processes in the cell. The model is chosen to
give the best possible match between the model's
impedance and the measured impedance
 Which is the best eqvt. ckt?
EIS spectrum
software packages to fit the spectra to
analogous circuits

possible eqvt ckts (ckt model

is not unique!)

•physical model should be verified!

•alter a single cell component (for
example increase a paint layer
thickness) and see if you get the
expected changes in the impedance
spectrum
• Application of perturbation- centered on
– free corrosion potential
– cathodic protection potential
 Validity of Spectra
• Before attempting to model impedance spectra,
be assured that the spectra are valid.
• When a sine wave is used as the perturbation,
the relationship between the current and applied
voltage can be characterized by
– the ratio between the amplitudes of the voltage and
the current => modulus of impedance
– and the phase shift between the rotating vectors
which represent the instantaneous voltage and
current.=> phase shift of the vector (a complex
number)
• In mathematical terms, the impedance is a
transfer function relating (the Laplace transform
of) a response (e.g., current) to (the Laplace
transform of) a perturbation (e.g., voltage).
 Conditions for validity
• The transfer function can only become an impedance
when the following four conditions are fulfilled:
1. Causality: The response of the system must be a result only of
the applied perturbation.
difficult to verify (ASTM => equipment & cell)
2. Linearity: The relationship between the perturbation and
response is independent of the magnitude of the perturbation.
easy, generate spectra using higher and lower magnitude and verify
the modulus and phase angle values
3. Stability: The system returns to its starting state after the
perturbation is removed.
generate spectra from high to low freq and then from low to high
freq. (low freq. can upset the system as it takes longest)
4. Finite valued: The transfer function (impedance) must be finite
as the frequency approaches both 0 and ∞ and is continuous
and finite valued at all intermediate frequencies.