1. EIS Spectrum Analyser

EIS Spectrum Analyser is a standalone program for analysis and simulation of impedance spectra. The analyser routine is based on algorithms of the PDEIS spectrometer. In the original (potentiodynamic) version the impedance data analysis is applied on a 3D spectrum and gives dependences of the ac response components on electrode potential.

This standalone program has been adapted to solve a wide range of tasks in the common (stationary) impedance spectroscopy. In addition to data fitting to equivalent circuits with resistors, capacitors, inductors, constant phase, Warburg (3 types), user-defined and Gerischer elements, the EIS Spectrum Analyser provides various tests for data consistency and quality of fit. It has also a built-in impedance spectra simulation routine, tools for impedance data processing (subtraction of circuit elements and subcircuits, normalisation for electrode surface area) and plotting in various formats. The program is free for noncommercial use.

See: http://www.abc.chemistry.bsu.by/vi/analyser/

2. ZsimpWin

ZSimpWin is a EIS Data Analysis program that does not require user-input on initial values. ZSimpWin is an Electrochemical Impedance Spectroscopy (EIS) Data Analysis Software integrated with the 
VersaStudio software to provide straightforward and versatile equivalent circuit model fitting.  Innovative concepts have been implemented to achieve the following performance:

• Minimal user input: The user specifies a job by selecting a model for an impedance data set, and simply requests execution to ZSimpWin.  
• Automatic analysis: Parameters associated with the selected model are determined automatically. ZSimpWin assigns an initial guess of these parameters (default = Auto Setup option), starts computation using the initial guess, finds results, improves these results a number of times until desired results are obtained, and then saves the final results. 
• Batch Analysis: Setup a batch by including multiple jobs and process in sequence.  
• Output results in various forms: Results consist of plots, estimated parameters, and historical records of computation process.  Each or several combinations can be printed or copied to Windows clipboard. 
  
• Requires only mouse button clicks:  The whole process requires no entry of numbers or character strings.                                                                
• Compatible with Windows 10, 8 , 7 and XP.

See: https://www.ameteksi.com/products/software/zsimpwin

3. Zview

ZView software from Scribner Associates offers best-in-class equivalent circuit modeling. Fit common circuits instantly, generate publication-quality graphs quickly. ZView integrates easily with SAI measurement softwares, and supports testing hardware from Solartron, PAR, and others. Increase your data processing efficiency quickly and easily with ZView.

See: https://sai-zview1.software.informer.com/3.4/

Introduction of EIS

Electrochemical impedance spectroscopy (EIS) is one of the most powerful methods in the study of corrosion. The EIS method can be used to measure the rate or rate of corrosion, monitor corrosion, determine coating integrity, and study the mechanism of reactions. In this article, which is a compilation, translation and purification of references [1] and [2], the applications, limitations and benefits of this method are introduced. EIS is usually performed by applying an AC current signal to a state-steady electrochemical system and then measuring the current response. Because the amount of disturbance applied, the AC signal, is a small excitation signal, EIS is essentially a non-destructive technique. To apply this method requires a geometrically corroded cell that includes a reference electrode, as well as equipment capable of measuring and recording the electrical response of an electrochemical cell over a wide range of applied AC frequencies. When a small sine voltage is applied to an electrochemical system according to Equation 9, a sine current response in the form of Equation 2 will be observed. Due to the lack of rapid response of relaxation processes or the release of dipoles, the rotation of bipolar components in response to the applied alternating electric field results in a phase change.

Typical measurements in EIS are usually made in a three-electrode system, as shown in Figure 9. The entire set includes an electrochemical cell, a frequency generator, a frequency response analyzer (FRA), and a computer that is used to control experiments and store information. A potentiostat is used to control the electrode potential. The FRA is the heart of the system that calculates the imaginary and real parts of impedance. The frequency studied is usually in the cell range. 0.01–100,000 Hz (cycles / s) Electrochemical, the test material is embedded as an electrode working. Electrode counters, which must be neutral and not involved in the electrochemical reaction, are usually made of Pt, gold, or graphite. Reference electrodes are usually conventional saturated calomel electrodes (SCE) or AgCl / Ag electrodes. However, in many applications, such as thin electrolyte layers or in high temperature environments, conventional reference electrodes do not work properly. In these cases, systems without conventional reference electrodes should be used. As an example, we can refer to the two-electrode system, which usually consists of two identical electrodes consisting of test materials (Figure 2-a) and is widely used in atmospheric corrosion monitoring [5. [Figure 2-b) Indicates that it is used to monitor high-corrosion corrosion. , Multi-electrode array (Figure 2-c) can be used for EIS monitoring.

An uncompensated electrolyte resistance (Rs), a specific capacitance value related to the coating applied to the metal surface (Cc), a hole resistance in the coating of resistance pathways (pore solution resistance) (Rcp) in the coating where ions are transported, a The specific capacitance corresponding to the double layer in the solution / metal (Cdl) and a resistance (Rp) which is the resistance of the charge transfer process (ie corrosion), and in other words, the resistance to polarization at the solution / metal interface. In Beaunier rectified circuits, usually other additional components, such as the constant phase element (CPE), the phase component of the inductance or induction coefficient (L) and the resistor (W (Warburg,) replace the resistor or capacitor. Special capacitance, accuracy and quality of experimental data fitting with these circuits are improved, but the physical interpretation of the results will be ambiguous, this is because the CPE module can not be easily obtained with capacitor capacitance, and the capacity power calculation is calculated. Capacitor from CPE parameters requires accurate knowledge of the physical reasons for CPE behavior [7.] An example of a Nyquist diagram and its equivalent wind diagram in doubt ل 4 is given. The position of the equivalent circuit components in these diagrams is given on each diagram. In addition to common, simple equivalent circuit models, more complex physical models are sometimes used to interpret EIS data obtained from more complex systems. An example is the line transmission model (TML), which was first used by Levie de in his research on porous electrodes [11] [TML model and its modified models for analyzing EIS data on atmospheric corrosion under electrolyte layers Thin [5] as well as stress corrosion [12] have been used.

Atmospheric corrosion is an electrochemical process that usually occurs beneath a thin electrolyte surface layer, in the presence or absence of salt contaminants and dissolved gases in these layers. It has been shown that the atmospheric corrosion rate of metals depends on the thickness of the electrolyte thin film. The thickness of the electrolyte layer affects the rate of oxygen transfer through the electrolyte layer and the dissolution of corrosion products. The rate of oxygen transfer determines the rate of cathodic reaction (in neutral and alkaline solutions) and the dissolution of corrosion products determines the anodic process. Monitoring or corrosion of thin electrolytic films using conventional electrochemical methods is challenging The electrolyte is thin, very high, leading to a sharp drop in ohmic potential and a non-uniform current distribution that makes it difficult to measure the corrosion rate [5. The solution resistance is estimated from the impedance measured in the high frequency range of the EIS spectrum, and the sum of the resistivity (Rp) and the solution resistance (RS) from the impedance in the low frequency range. Figure 4b: The calculated resistive palliation is then converted to the corrosion rate of the metal. To study atmospheric corrosion of the metal surface under thin electrolytic layers (100010-1000 ~) by EIS, it is possible to expose the corrosion cell to the atmosphere. weather Use outside or use laboratory-drier simulation cycles [19–13,10,9,5. Used in epoxy resin (Figure 2-A) to make cells. The study can be done in two ways: either the impedance spectrum is recorded over a wide range of applied frequencies or the impedance value is checked continuously at two constant frequencies. The study of EIS spectrum in a wide frequency range has shown that a one-dimensional equivalent circuit model called TML can be used to model the corrosion rate in these systems [5. Palrization is calculated from the impedance difference measured at the above two frequencies. The corrosion rate is then calculated using the polarization resistance [5]. Nishikata et al. [5] also used shoulder-shaped electrodes to study atmospheric corrosion to EIS. Impedance information was monitored at 10 mHz and 10 kHz. The results showed that the inverse of the mean impedance at low frequency completely corresponds to the corrosion rate obtained by gravimetry. Wetting of Time also occurs when the amount of solution conductivity or high frequency impedance image (Rs image) exceeds a threshold value. One of the disadvantages of this method in the study of atmospheric corrosion is that if the metal surface is covered with a thick layer of corrosion products, the low frequency impedance can not be equated to the polarization resistance. Finally, Ma et al. [20] used a complex multi-electrode system to study atmospheric corrosion and found the results to be more accurate than two-electrode systems. 3.2 Corrosion of reinforced concrete Rebar (in concrete is the main reason for reducing the life of reinforced concrete structures that are exposed to strong corrosive environments) such as marine environment. Therefore, reinforcement corrosion monitoring is very important to assess the health status of reinforced concrete. Various methods are used to evaluate corrosion in reinforced concrete, and electrochemical methods are among the most common. Among these, EIS is an attractive technique because, as mentioned earlier, it is almost a non-destructive method. In addition, EIS is suitable for environments with very high strength, such as concrete, because it is essentially a transient method and does not require the system to be in a stable state [21. [In steel systems (reinforcement) / Concrete, information Various parameters such as the presence of surface films, concrete properties, joint joint corrosion and mass transfer phenomena can be obtained from the EIS method [21. [22] [In addition, the high-frequency impedance of information in Moore Provides dielectric properties of concrete, and low-frequency impedance information on the properties of passive films (surface oxide layers) on steel. Studies that began three decades ago have proven the validity of EIS as a technique for studying rebar corrosion in concrete, both experimentally and theoretically. John et al. (9189) monitored corrosion of rebar in high porosity concrete using EIS. They obtained both the corrosion rate of the steel rebars and the information on the steel surface layers. Later, more fundamental work was done by McDonald et al. To establish the application of EIS in the detection of rebar corrosion in concrete [3]. In this work, the rebar was simulated as a one-dimensional electrical transmission line. Their results show that imaginary and real components of impedance and phase angle can be used to detect corrosion of rebar embedded in concrete, but this is only possible at very low frequencies (for example, 1 mHz). It was also found that monitoring the peak voltage at the concrete surface just above the rebar helps to fully detect corrosion.

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Interaction of an electron beam with a sample target produces a variety of emissions, including x-rays. An energy-dispersive (EDS) detector is used to separate the characteristic x-rays of different elements into an energy spectrum, and EDS system software is used to analyze the energy spectrum in order to determine the abundance of specific elements. EDS can be used to find the chemical composition of materials down to a spot size of a few microns, and to create element composition maps over a much broader raster area. Together, these capabilities provide fundamental compositional information for a wide variety of materials.

How it Works – EDS

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EDS systems are typically integrated into either an SEM or EPMA instrument. EDS systems include a sensitive x-ray detector, a liquid nitrogen dewar for cooling, and software to collect and analyze energy spectra. The detector is mounted in the sample chamber of the main instrument at the end of a long arm, which is itself cooled by liquid nitrogen. The most common detectors are made of Si(Li) crystals that operate at low voltages to improve sensitivity, but recent advances in detector technology make availabale so-called “silicon drift detectors” that operate at higher count rates without liquid nitrogen cooling.

An EDS detector contains a crystal that absorbs the energy of incoming x-rays by ionization, yielding free electrons in the crystal that become conductive and produce an electrical charge bias. The x-ray absorption thus converts the energy of individual x-rays into electrical voltages of proportional size; the electrical pulses correspond to the characteristic x-rays of the element.

Strengths

• When used in “spot” mode, a user can acquire a full elemental spectrum in only a few seconds. Supporting software makes it possible to readily identify peaks, which makes EDS a great survey tool to quickly identify unknown phases prior to quantitative analysis.
• EDS can be used in semi-quantitative mode to determine chemical composition by peak-height ratio relative to a standard.

Limitations

• There are energy peak overlaps among different elements, particularly those corresponding to x-rays generated by emission from different energy-level shells (K, L and M) in different elements. For example, there are close overlaps of Mn-K_α and Cr-K_β, or Ti-K_α and various L lines in Ba. Particularly at higher energies, individual peaks may correspond to several different elements; in this case, the user can apply deconvolution methods to try peak separation, or simply consider which elements make “most sense” given the known context of the sample.
• Because the wavelength-dispersive (WDS) method is more precise and capable of detecting lower elemental abundances, EDS is less commonly used for actual chemical analysis although improvements in detector resolution make EDS a reliable and precise alternative.
• EDS cannot detect the lightest elements, typically below the atomic number of Na for detectors equipped with a Be window. Polymer-based thin windows allow for detection of light elements, depending on the instrument and operating conditions.

Results

A typical EDS spectrum is portrayed as a plot of x-ray counts vs. energy (in keV). Energy peaks correspond to the various elements in the sample. Generally they are narrow and readily resolved, but many elements yield multiple peaks. For example, iron commonly shows strong K_α and K_βpeaks. Elements in low abundance will generate x-ray peaks that may not be resolvable from the background radiation.

EDS spectrum of multi-element glass (NIST K309) containing O, Al, Si, Ca, Ba and Fe (Goldstein et al., 2003). Details

EDS spectrum of biotite, containing detectable Mg, Al, Si, K, Ti and Fe (from Goodge, 2003). Details

References

• Severin, Kenneth P., 2004, Energy Dispersive Spectrometry of Common Rock Forming Minerals. Kluwer Academic Publishers, 225 p.–Highly recommended reference book of representative EDS spectra of the rock-forming minerals, as well as practical tips for spectral acquisition and interpretation.
• Goldstein, J. (2003) Scanning electron microscopy and x-ray microanalysis. Kluwer Adacemic/Plenum Pulbishers, 689 p.
• Reimer, L. (1998) Scanning electron microscopy : physics of image formation and microanalysis. Springer, 527 p.
• Egerton, R. F. (2005) Physical principles of electron microscopy : an introduction to TEM, SEM, and AEM. Springer, 202.
• Clarke, A. R. (2002) Microscopy techniques for materials science. CRC Press (electronic resource)

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Electrochemical Impedance Spectroscopy (EIS) is a powerful tool enabling the study of processes that occur at the interface of an electrode.

In EIS a periodic signal is applied in current or voltage at several frequencies. The periodic signal is traditionally built with a sinus.
The transfer function H of the system is defined as:

H(s)=L[Output(t)]L[Input(t)]H(s)=ℒ[Output(t)]ℒ[Input(t)] (1)

ℒ  being the Laplace transform

Measurements as a function of the frequency of the perturbation give an impedance, Z,  (or admittance) diagram. The impedance is given in Ohm as it is the ratio of the voltage vs. the current and is a complex number.

To be valid, the system under study has to be:

• Linear: The response (output) of the cell has to be directly proportional to the input. The small perturbation of the electrode state has the advantage that the solutions of relevant mathematical equations used are transformed in linear forms.
• Time invariant: The state of the cell must not change during the measurements.
• Causal: The output has to be correlated directly with the input.

The modulus Z and phase Phi are the parameters of interest, so the impedance data can be plotted in Bode plot (Z and Phi vs frequency), but in electrochemistry, the most common plot is the Nyquist plot -Im(Z) vs Re(Z).

As the periodical perturbation is performed at several frequencies, EIS is capable of characterizing processes that have different time constants i.e. fast process at high frequency (> 10 kHz) and low process such as diffusion at low frequencies (<100 mHz).

Consider Ohm’s law, which describes the relationship of voltage to a direct current passing through a resistor:

E=IRE=IR

Impedance is, very simply, extends the concept of resistance to an alternating current circuit, and generally represented as ZZ. So you can think of it, simply, like this:

E=IZZE=IZZ

We’ll come back to this in a moment. For now, it should be clear that a measurement of impedance, therefore, can be made by made simply by applying an oscillating voltage, and measuring the (oscillating) current response. We can write down an equation for the oscillating voltage we apply like so:

E(t)=|E|sin(ωt)E(t)=|E|sin⁡(ωt)

where |E||E| is the amplitude of the voltage signal, and ω=2πfω=2πf (the angular frequency). The response will be a current with an amplitude |I||I|, which is also shifted in phase from the applied signal:

I(t)=|I|sin(ωt+θ)I(t)=|I|sin⁡(ωt+θ)

The current is shifted in phase because of reactance (e.g., a capacitance or inductance) in addition to the resistance (which changes the amplitude). The impedance can therefore be expressed like this:

ZZ=E(t)I(t)=|E|sin(ωt)|I|sin(ωt+θ)=|Z|sin(ωt)sin(ωt+θ)ZZ=E(t)I(t)=|E|sin⁡(ωt)|I|sin⁡(ωt+θ)=|Z|sin⁡(ωt)sin⁡(ωt+θ)

Have a look at the animation below. The ‘current’, I, is 72° out of phase with the ‘voltage’. The graph on the right is known as a Lissajous curve, showing the relationship between I and E. In the past, impedance spectroscopy was done by obtaining these curves on an oscilloscope and analysing them. Thankfully, it’s all a bit easier nowadays.

Complex representation

Ok, complex maths time. Without going into too much detail, via Euler’s formula:

ejx=cos(x)+jsin(x)ejx=cos⁡(x)+jsin⁡(x)

we can re-write all of the above using complex numbers:

ZZ=|Z|ejθ=|E|ejωt|I|ejωt+θZZ=|Z|ejθ=|E|ejωt|I|ejωt+θ

or simply:

EE=IZZ=I|Z|ejθEE=IZZ=I|Z|ejθ

Note that jj is the imaginary unit, i.e., j=√−1j=−1, which we use instead of ii to avoid confusion with the symbol for electrical current. You can see from the above equation that the ratio of an oscillating voltage to an oscillating current is the impedance, which has a magnitude |Z||Z| and a phase angle θθ. You can think of this as a polar coordinate representation. More commonly for impedance spectroscopy, however, we generally use the Cartesian complex plane representation, dividing the complex impedance into the real and imaginary parts:

ZZ=Z′+jZ′′ZZ=Z′+jZ″

Z′Z′ and Z′′Z″ are the resistive and reactive parts of the impedance respectively. You’ll see this more clearly on the page about the impedance of simple RC circuits.

We can represent any ZZZZ on an Argand diagram, as in the graph below. This is the basis for the Nyquist plot, which is the plot of the real and imaginary parts of the impedance that you’ll come across most often. An impedance measurement for a single frequency is a single point on a Nyquist plot. An impedance spectrum is therefore a series of points, where each point is a different frequency.

These plots are visually useful, because the characteristic shapes that can appear in the plots as you’ll see later can give you a rough idea of what you’re looking at. The downside, though, is that you can’t know what the frequency associated with a particular point is from looking at the Nyquist plot alone, and so the plot doesn’t contain all the information you need. This is why the alternative Bode plot – plots of logZ′log⁡Z′ and logZ′′log⁡Z″ vs logflog⁡f, or log|Z|log⁡|Z| and θθ vs logflog⁡f – are still important.

Nyquist plot

I’ll finish up this page by briefly introducing a typical Nyquist representation of an impedance spectrum itself. The plot below is data I acquired from a Li-ion test battery, and fitted to a model myself. The frequency range the points represents is between 100 kHz and 100 mHz. This is fairly typical for most systems, although depending on what you want to measure you might go up to 1 MHz or more, or as low as 1 mHz. So how do you make sense of this plot? Well, there are three things I’ll note for now.

First, the impedance is always lowest (i.e., smallest values of |Z||Z| at the highest frequency, so you can see that the frequency decreases if we follow the curve from the points near the origin to the points in the top-right corner. Secondly, you’ll note (as in the Argand diagram above) that the values of Z′′Z″ are negative (plotted as −Z′′−Z″). This will become clearer later, but by convention capacitance is a negative reactance, so impedance spectra will in most cases only have positive Z′Z′ values and negative Z′′Z″ values.

Lastly, you’ll note the shape of the spectrum, particularly the semi-circle part. The shapes you see in the Nyquist plots can be characteristic of certain elements or combinations of elements, so they are (often, but not always) visually useful for quickly understanding something about the system you’re measuring. Because of this I was able to take this relatively good quality data, think of a reasonable model, guess a few of the parameters and then fit the entire spectrum relatively quickly. In the following pages you’ll read about the experimental technique I used to get this data as well as the elements of the model I’ve fitted the data to, and hopefully you’ll be able to see how it all fits together.

Orthonormal scales should be used for Nyquist impedance plots. The length from 0 to 1 along the imaginary axis should be equal to the length from 0 to 1 along the real axis. Otherwise, semicircle graphs are not semicircles (Fig. 1) and it becomes difficult to measure angles (Fig. 2). We present here two examples: the impedance for a Tafelian redox system (Fig. 1) and the Randles circuit with Warburg impedance (Fig. 2). Orthonormal and non-orthonormal plots are compared: non-orthonormal scales are indicated by a sad face and the orthonormal scale is indicated by a happy face. More details in the corresponding Mathematica Demonstration [1].

EIS accuracy contour plots must be used to interpret errors made during EIS measurements and identify the best frequencies possible to be used for a given impedance range. The aim of Fig. 1 is to demonstrate how to read and understand EIS accuracy contour plots provided with each potentiostat .

Fig 1: Superimposition of EIS accuracy contour plot and modulus
Bode diagram of R1+R2/C2  electrical circuit (left) and Nyquist diagram
of the same circuit (right).

The different colored areas show different ranges of impedances that can be measured at various frequencies within a specified error in magnitude (%) and in phase (°).

The accuracy contour plot is an image of the capability of the instrument and is only valid for a given set of conditions (input amplitude, temperature, data averaging, etc).