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Introduction.
Electrochemical impedance spectroscopy is a recent tool in corrosion and solid state laboratories that is slowly making its way into the service environment as units are decreased in size and become portable. Impedance Spectroscopy is also called AC Impedance or just Impedance Spectroscopy. The usefulness of impedance spectroscopy lies in the ability to distinguish the dielectric and electric properties of individual contributions of components under investigation.
Below is a listing of the advantages and disadvantages of the technique. Advantages. 1. Useful on high resistance materials such as paints and coatings. 2. Time dependent data is available 3. Non- destructive. 4. Quantitative data available. 5. Use service environments.
1. AC Circuit Theory and Representation of Complex Impedance Values. 2. Physical Electrochemistry and Circuit Elements. 3. Common Equivalent Circuit Models. 4. Extracting Model Parameters from Impedance Data. 5. Case studies
Ohm's law defines resistance in terms of the ratio between voltage E and current I.
E (t ) R! I (t )
The relationship is limited to only one circuit element -- the ideal resistor. An ideal resistor has several simplifying properties: It follows Ohm's Law at all current and voltage levels It's resistance value is independent of frequency. AC current and voltage signals though a resistor are in phase with each other
Real World:
Circuit elements that exhibit much more complex behavior. These elements force us to abandon the simple concept of resistance. In its place we use impedance, which is a more general circuit parameter. Like resistance, impedance is a measure of the ability of a circuit to resist the flow of electrical current. Unlike resistance, impedance is not limited by the simplifying properties listed above. Electrochemical impedance is usually measured by applying an AC potential to an electrochemical cell and measuring the current through the cell. Suppose that we apply a sinusoidal potential excitation. The response to this potential is an AC current signal, containing the excitation frequency and it's harmonics. This current signal can be analyzed as a sum of sinusoidal functions (a Fourier series). Electrochemical Impedance is normally measured using a small excitation signal. This is done so that the cell's response is pseudo-linear. Linearity is described in more detail in a following section. In a linear (or pseudo-linear) system, the current response to a sinusoidal potential will be a sinusoid at the same frequency but shifted in phase.
The excitation signal, expressed as a function of time, has the form of:
E (t ) ! E0 cos([t )
E(t) is the potential at time tr Eo is the amplitude of the signal, and [ is the radial frequency. The relationship between radial frequency [ (expressed in radians/second) and frequency f (expressed in Hertz (1/sec).
[ =2T f
An expression analogous to Ohm's Law allows us to calculate the admittance (=the AC resistance) of the system :
Z (t ) !
The impedance is therefore expressed in terms of a magnitude, Z0, and a phase shift, f. This admittance may allso be written as complex function:
Measure Z([,Vbias)
If we plot the applied sinusoidal signal on the X-axis of a graph and the sinusoidal response signal I(t) on the Y-axis, an oval is plotted. This oval is known as a "Lissajous figure". Analysis of Lissajous figures on oscilloscope screens was the accepted method of impedance measurement prior to the availability of lock-in amplifiers and frequency response analyzers.
Complex writing
Z (t ) ! E (t ) E0 cos([t ) cos([t ) ! ! Z0 I (t ) I 0 cos([t J ) cos([t J )
it is possible to express the impedance as a complex function. The potential is described as,
E (t ) ! E0 exp( j[t )
and the current response as,
I (t ) ! I 0 exp(i[t iJ )
1 1 1 ! Z R i[C
On the Nyquist plot the impedance can be represented as a vector of length |Z|. The angle between this vector and the xaxis is f. Nyquist plots have one major shortcoming. When you look at any data point on the plot, you cannot tell what frequency was used to record that point. Low frequency data are on the right side of the plot and higher frequencies are on the left. This is true for EIS data where impedance usually falls as frequency rises (this is not true of all circuits).
The Nyquist plot the results from the RC circuit. The semicircle is characteristic of a single "time constant". Electrochemical Impedance plots often contain several time constants. Often only a portion of one or more of their semicircles is seen.
Another popular presentation method is the "Bode plot". The impedance is plotted with log frequency on the x-axis and both the absolute value of the impedance (|Z| =Z0 ) and phase-shift on the y-axis. The Bode plot for the RC circuit is shown below. Unlike the Nyquist plot, the Bode plot explicitly shows frequency information.
Electrical circuit theory distinguishes between linear and non-linear systems (circuits). Impedance analysis of linear circuits is much easier than analysis of non-linear ones. A linear system ... is one that possesses the important property of superposition: If the input consists of the weighted sum of several signals, then the output is simply the superposition, that is, the weighted sum, of the responses of the system to each of the signals. Mathematically, let y1(t) be the response of a continuous time system to x1(t) ant let y2(t) be the output corresponding to the input x2(t). Then the system is linear if: 1) The response to x1(t) + x2(t) is y1(t) + y2(t) 2) The response to ax1(t) is ay1(t) ...
However, we will show how electrochemical systems can be pseudo-linear. When you look at a small enough portion of a cell's current versus voltage curve, it seems to be linear. In normal EIS practice, a small (1 to 10 mV) AC signal is applied to the cell. The signal is small enough to confine you to a pseudo-linear segment of the cell's current versus voltage curve. You do not measure the cell's nonlinear response to the DC potential because in EIS you only measure the cell current at the excitation frequency.
Time
Amplitude
Frequency
Use the Fourier transform and inverse Fourier transform to switch between the domains. The common term, FFT, refers to a fast, computerized implementation of the Fourier transform. Detailed discussion of these transforms is beyond the scope of this manual. Several of the references given at the end of this chapter contain more information on the Fourier transform and its use in EIS. In modern EIS systems, lower frequency data are usually measured in the time domain. The controlling computer applies a digital approximation to a sine wave to the cell by means of a digital to analog converter. The current response is measured using an analog to digital computer. An FFT is used to convert the current signal into the frequency domain.
Notice that the impedance of a resistor is independent of frequency and has only a real component. Because there is no imaginary impedance, the current through a resistor is always in phase with the voltage. The impedance of an inductor increases as frequency increases. Inductors have only an imaginary impedance component. As a result, an inductor's current is phase shifted 90 degrees with respect to the voltage. The impedance versus frequency behavior of a capacitor is opposite to that of an inductor. A capacitor's impedance decreases as the frequency is raised. Capacitors also have only an imaginary impedance component. The current through a capacitor is phase shifted -90 degrees with respect to the voltage.
Very few electrochemical cells can be modeled using a single equivalent circuit element. Instead, EIS models usually consist of a number of elements in a network. Both serial and parallel combinations of elements occur.
Z eq ! Z1 Z 2 Z3
1 1 1 1 ! Z eq Z1 Z 2 Z3
R1
R2
Z eq ! Z1 Z 2 ! R1 R 2 ! 1; 4; ! 5;
Resistance and impedance both go up when resistors are combined in series. Now suppose that we connect two 2 F capacitors in series. The total capacitance of the combined capacitors is 1 F
C1
C2
Impedance goes up, but capacitance goes down when capacitors are connected in series. This is a consequence of the inverse relationship between capacitance and impedance.
2 Zn ! 2 Zn 2 4e
2.The reaction at the cathode between water and electrons
O2 4 H 4e ! 2 H 2O
3.The reaction of the whole cell, i.e. the two half-cell reactions added together:
2 Zn O2 4 H ! 2 Zn 2 2 H 2O
(G is the free energy change of the reaction. (G0 is what the free energy change would be if every component were in its standard state. ax is the activity of reaction product X and ay is the activity of reactant Y. nx is the stoichiometric coefficient of reaction product X, and likewise for the reactants.(The stoichiometric coefficient is the number of that molecule that are involved in the reaction; for the whole-cell reaction written above, the stoichiometric coefficient of water is 2, and of oxygen gas is 1.) R is the ideal gas constant and T is the temperature. The symbol 4 is the multiplying equivalent of 7 : all the terms after it are multiplied together.
!k
where K is the equilibrium constant. Thus we can deduce that (G0 =RTlnk ; this is true of a reaction whether it is at equilibrium or not. ((G0 for a reaction is determined by the energies of the bonds within the molecules of the reactants and products, and this is independent of how many such molecules there are per unit volume.)
(G {0 and the quotient is not the equilibrium constant but equal to the electric potential. We can convert this into an expression for the electrical potentials using the general rule:
(G ! zFE
where z is the stoichiometric number of electrons in the reaction. (This is due to Faradays law)
The activities of Zn and water are one, because Zn is in its standard state and the water is so much more abundant than its solutes that it may as well be in its standard state. Thus:
2 1/ Ee ! E 0 RT ln aZn2 a H pO22
E0 is the equilibrium potential it is the potential of the whole cell when the electrodes are at equilibrium within themselves. It can be worked out (easily, using algebra with a pen and pencil) that:
RT ln k zF where K is the equilibrium constant i.e. if we were at equilibrium over the whole electrochemical cell, then E would be zero. E0 is a property of the system like that (G0 , and is still equal to the same number even when the whole cell is not at equilibrium. If for some reason it was required to find the value of E0 , we could use this expression. E0 is called the standard electrode potential. E0 !
l A where r is the solution resistivity. The conductivity of the solution, W , is more commonly used in solution resistance calculations. R!V Its relationship with solution resistance is: 1 l l R= W RA W A
Polarization Resistance
Whenever the potential of an electrode is forced away from it's value at open circuit, that is referred to as polarizing the electrode. When an electrode is polarized, it can cause current to flow via electrochemical reactions that occur at the electrode surface. The amount of current is controlled by the kinetics of the reactions and the diffusion of reactants both towards and away from the electrode. In cells where an electrode undergoes uniform corrosion at open circuit, the open circuit potential is controlled by the equilibrium between two different electrochemical reactions. One of the reactions generates cathodic current and the other anodic current. The open circuit potential ends up at the potential where the cathodic and anodic currents are equal. It is referred to as a mixed potential. The value of the current for either of the reactions is known as the corrosion current.
The Butler Volmer equation: For the polarization resistance of simple reactions at electrodes
When there are two simple, kinetically controlled reactions occurring, the potential of the cell is related to the current by the following (known as the Butler-Volmer equation).
I is the measured cell current in amps, Icorr is the corrosion current in amps, Eoc is the open circuit potential in volts, Fa is the anodic Beta coefficient in volts/decade, Fc is the cathodic Beta coefficient in volts/decade If we apply a small signal approximation (E-Eoc is small) to the buler Volmer equation, we get the following:
which introduces a new parameter, Rp, the polarization resistance. As you might guess from its name, the polarization resistance behaves like a resistor. If the Tafel constants Fi are known, you can calculate the Icorr from Rp. The Icorr in turn can be used to calculate a corrosion rate. We will further discuss the Rp parameter when we discuss cell models.
or more generally: In the forward reaction in the first equation, electrons enter the metal and metal ions diffuse into the electrolyte. Charge is being transferred. This charge transfer reaction has a certain speed. The speed depends on the kind of reaction, the temperature, the concentration of the reaction products and the potential. The general relation between the potential and the current holds:
io = exchange current density Co = concentration of oxidant at the electrode surface Co* = concentration of oxidant in the bulk CR = concentration of reductant at the electrode surface
F = Faradays constant T = temperature R = gas constant a = reaction order n = number of electrons involved h = overpotential ( E - E0 )
Overvoltage potential
The overpotential, h, measures the degree of polarization. It is the electrode potential minus the equilibrium potential for the reaction. When the concentration in the bulk is the same as at the electrode surface, Co=Co* and CR=CR*. This simplifies the last equation into:
This equation is called the Butler-Volmer equation. It is applicable when the polarization depends only on the charge transfer kinetics. Stirring will minimize diffusion effects and keep the assumptions of Co=Co* and CR=CR* valid. When the overpotential, h, is very small and the electrochemical system is at equilibrium, the expression for the charge transfer resistance changes into:
From this equation the exchange current i0 density can be calculated when Rct is known.
On a Nyquist plot the infinite Warburg impedance appears as a diagonal line with a slope of 0.5. On a Bode plot, the Warburg impedance exhibits a phase shift of 45. In the above equation, s is the Warburg coefficient defined as:
[ = radial frequency DO = diffusion coefficient of the oxidant DR = diffusion coefficient of the reductant A = surface area of the electrode n = number of electrons transferred C* = bulk concentration of the diffusing species (moles/cm3)
with, H = Nernst diffusion layer thickness D = an average value of the diffusion coefficients of the diffusing species This more general equation is called the "finite" Warburg. For high frequencies where [pg , or for an infinite thickness of the diffusion layer where d pg , this equation becomes the infinite Warburg impedance.
Coating Capacitance
A capacitor is formed when two conducting plates are separated by a non-conducting media, called the dielectric. The value of the capacitance depends on the size of the plates, the distance between the plates and the properties of the dielectric. The relationship is: II A C! 0 r d
With, Io = electrical permittivity Ir = relative electrical permittivity A = surface of one plate d = distances between two plates Whereas the electrical permittivity is a physical constant, the relative electrical permittivity depends on the material. Some useful Ir values are given in the table: Material vacuum water organic coating Ir 1 80.1 ( 20 C ) 4-8
Notice the large difference between the electrical permittivity of water and that of an organic coating. The capacitance of a coated substrate changes as it absorbs water. EIS can be used to measure that change
Constant Phase Element (for double layer capacity in real electrochemical cells)
Capacitors in EIS experiments often do not behave ideally. Instead, they act like a constant phase element (CPE) as defined below.
Z ! A(i[ ) E
When this equation describes a capacitor, the constant A = 1/C (the inverse of the capacitance) and the exponent E = 1. For a constant phase element, the exponent a is less than one.
The "double layer capacitor" on real cells often behaves like a CPE instead of like a capacitor. Several theories have been proposed to account for the non-ideal behavior of the double layer but none has been universally accepted. In most cases, you can safely treat E as an empirical constant and not worry about its physical basis.
Equivalent Admittance element 1/R R i[C C 1/i[L L Y0(i[)1/2 W (infinite Warburg) O (finite Warburg) Y0 i[ coth( B i[ ) Y0(i[)E Q (CPE)
Impedance
R 1/1/i[C i[L 1/Y0(i[)1/2
tanh( B i[ ) / Y0 i[
1/Y0(i[)E
The model includes a resistor (due primarily to the electrolyte) and the coating capacitance in series. A Nyquist plot for this model is shown in the Figure. In making this plot, the following values were assigned: R = 500 ; (a bit high but realistic for a poorly conductive solution) C = 200 pF (realistic for a 1 cm2 sample, a 25 m coating, and Ir = 6 ) fi = 0.1 Hz (lowest scan frequency -- a bit higher than typical) ff = 100 kHz (highest scan frequency)
The value of the capacitance cannot be determined from the Nyquist plot. It can be determined by a curve fit or from an examination of the data points. Notice that the intercept of the curve with the real axis gives an estimate of the solution resistance. The highest impedance on this graph is close to 1010 ; . This is close to the limit of measurement of most EIS systems
The diameter corresponds to the resistance R. The frequency at the 90 position corresponds to 1/t = 1/RC
Analyzing Circuits
By using the various Cole-Cole plots we can calculate values of the elements of the equivalent circuit for any applied bias voltage
By doing this over a range of bias voltages, we can obtain: the field distribution in the layers of the device (potential divider) and the relative widths of the layers, since C ~ 1/d
Randles Cell
The Randles cell is one of the simplest and most common cell models. It includes a solution resistance, a double layer capacitor and a charge transfer or polarization resistance. In addition to being a useful model in its own right, the Randles cell model is often the starting point for other more complex models. The equivalent circuit for the Randles cell is shown in the Figure. The double layer capacity is in parallel with the impedance due to the charge transfer reaction
The Nyquist plot for a Randles cell is always a semicircle. The solution resistance can found by reading the real axis value at the high frequency intercept. This is the intercept near the origin of the plot. Remember this plot was generated assuming that Rs = 20 ; and Rp= 250 ; . The real axis value at the other (low frequency) intercept is the sum of the polarization resistance and the solution resistance. The diameter of the semicircle is therefore equal to the polarization resistance (in this case 250; ).
Bode plot
The Bode plot for the same data is shown here. The lower frequency limit was moved down to 1mHz to better illustrate the differences in the slope of the magnitude and in the phase between the capacitor and the Warburg impedance. Note that the phase approaches 45 at low frequency.
Case studies
1. Relaxation Dispersion of O2- Ionic Conductivity in a ZrO0.85Ca0.15O1.85 Single Crystal 2. Effect of intergranular glass films on the electrical conductivity of 3Y-TZP
The relaxation dispersion regions of the ionic conductivity shift towards higher frequencies with increasing temperature. This indicates that these dispersions are thermally activated. At low temperatures the intragrain relaxation process in the zirconia lattice can be seen at high frequencies, but the electrode effects are too slow to be detected. In the temperature range from 673 K to 873K both dispersions of the electrodes and the bulk material are observed in the frequency range between 20 and 106 Hz. At higher temperatures the effect 0f the intragrain processes disappears and only the dispersion of the electrodes can be seen in the middle of the frequency window.
The relaxation dispersion regions of the ionic conductivity shift towards higher frequencies with increasing temperature. This indicates that these dispersions are thermally activated. At low temperatures the intragrain relaxation process in the zirconia lattice can be seen at high frequencies, but the electrode effects are too slow to be detected. In the temperature range from 673 K to 873K both dispersions of the electrodes and the bulk material are observed in the frequency range between 20 and 106 Hz. At higher temperatures the effect 0f the intragrain processes disappears and only the dispersion of the electrodes can be seen in the middle of the frequency window.
TZP 3Y
Specimens were round pellets oft ca 1.5 cm in diameter and 5 mm in height oft sintered ceramics oft TZP with varous amounts oft SiO2 and Al2O3 additions . The coprecipitated powders were calcined at 1050 C reground and pressed and then sintered at 1500C to full density. The pellets were carefully lapped to have planar faces and contacted with sintered Pt paste (without glass additive!!!)
Usually it is not possible to observe all three dispersions simultaneously, due to a limited frequency range used in this study (40 Hz-l MHz). At temperatures below 500 K only the grain dispersion can be seen at high frequencies.4o The grain boundary and the electrode dispersion are too slow to be detected at this temperature. In the medium temperature range (500 K-800 K), we can observe two dispersions, that of the grains and that of the grain boundaries. Finally, above 800 K the intragrain dispersion shifts out of the frequency window and the sluggish dispersion due to the slower electrode processes becomes visible.
In Fig. 3 the frequency dependence of the specific imaginary impedance contribution, p fI = Z" . LIA, is shown. From this figure the individual dispersion regions of grains, grain boundaries, and electrodes can be seen more distinctly. The complex impedance data can be displayed in the complex impedance plane with real part V' as the abscissa and the imaginary part V as the ordinate (Cole Cole diagram). A typical complex impedance spectrum of 3Y-TZP (sample E-10) at a medium temperature of 596 K is shown in Fig. 4.
Since the time constants (X = RC) of individual RC-elements differ by orders of magnitude, individual semicircles of the grains and that of the grain boundaries can clearly be distinguished in this temperature range. The real specific impedance sections between the distinct minima in the imaginary part V reveal the macroscopic specific resistivities of the grains (V G) and the grain boundaries (V'B), respectively. The macroscopic specific resistivity of the grain boundaries is equal to the difference between the total (dc) specific resistivity of the sampie (p T) and the macroscopic specific resistivity of the grains: VGB = VT - VG. Moreover, from the maximum of imaginary impedance V at the top of each semicircle, the relaxation frequency [ of the corresponding process can be determined from the relation [X= 1, where [ = 2Trfr, is the angular frequency [rad' s-1], fr the corresponding frequency of the applied electrical ac-field [Hz], and X = RC the time constant of the relaxation circuit.
Result: 3 mol Y TZP zirconia specimens with a ratio of 1:1 of SiO2 to Al2O3 impurities have highest grain boundary resistances