Electrochemical Noise

-0.363 2E-07 1.5E-07 1E-07 5E-08 0 1200

-0.3632 -0.3634 -0.3636 -0.3638 -0.364 -0.3642 -0.3644 0 400 800 Time (secs)

C u rre n t (A )

-0.3628

P o te n tia l ( V /S C E )

Electrochemical Noise Measurement

2.5E-07

Potential Current

Steel in 0.05M Ca(OH)2 + 0.1M NaCl

Potential Noise
Measured as potential difference between two nominally identical electrodes, or relative to a reference electrode (usually assumed to be noiseless).

Measurement Methods 1 - Potential Noise

Working Electrode

Reference Electrode

Terminology - Potential Noise

Instantaneous noise potential,

En E E
Potential noise power (= variance of signal)

E EE
2 n

Potential noise standard deviation

E
2 n

E E

Potential Noise
First shown to be related to corrosion rate by Iverson in 1968. Recent theoretical work suggests that the potential noise is larger for less frequent, and hence more localized events, such as metastable pitting corrosion

Current Noise
Usually measured as galvanic current flowing between two nominally identical electrodes, although potentiostatic measurements can be made.

Measurement Methods 2 - Current Noise

Zero Resistance Ammeter A

Working Electrode 1

Working Electrode 2

Terminology - Current Noise

Instantaneous noise current,

In I I
Current noise power (= variance of signal)

In2 ( I I )2
Current noise standard deviation

I II
2 n

Current Noise
Standard deviation of current is usually found to increase as corrosion rate increases.

Noise Resistance
Obtained by dividing standard deviation of potential noise by standard deviation of current noise, measured at the same time, to produce Rn.

Measurement Methods 3 - Noise Resistance

Zero Resistance Ammeter A

Working Electrode 1

Working Electrode 2

Reference Electrode

Noise Resistance
Rn is expected to be equivalent to the linear polarization resistance, Rp. Hence often gives good quantitative estimate of corrosion rate using the Stern-Geary equation. There are questions about the effective measurement frequency.

Sources of Noise
Active dissolution (or other electrochemical reaction) Pit nucleation, propagation and death Hydrogen bubble evolution Mass transport fluctuations Mains frequency interference Electronic noise Vibration

-0.363 2E-07 1.5E-07 1E-07 5E-08 0 1200

-0.3632 -0.3634 -0.3636 -0.3638 -0.364 -0.3642 -0.3644 0 400 800 Time (secs)

C u rre n t (A )

-0.3628

P o te n tia l ( V /S C E )

Crevice Corrosion
2.5E-07

Potential Current

Mild steel in 0.05 M Ca(OH)2 + 0.1 M NaCl

P o te n tia l ( V /S C E )

Pitting Corrosion
8E-08 7E-08 6E-08 5E-08 4E-08 3E-08 1200
C u rre n t (A )

-0.272 -0.273 -0.274 -0.275 -0.276 0 200 400 600 800 Time (secs) 1000

9E-08

-0.2725 -0.2735 -0.2745 -0.2755

Potential Current

mild steel in 0.05 M Ca(OH)2 + 0.025 M NaCl

Correlation of E and I
P o t e n t ia l (V / S C E )
P o t e n t ia l (V / S C E )

-0.3635 -0.3636 -0.3637 -0.3638 -0.3639 -0.364 -0.3641 -0.3642 -0.3643 0

2.5E-07
C u rre n t (A )

-0.2735 -0.274

8E-08 7E-08 6E-08 5E-08 4E-08

C u rre n t (A )

2E-07 1.5E-07 1E-07 5E-08 10 20 30 40 50 60 Time (s)

-0.2745 -0.275

-0.2755

-0.276 3E-08 100 110 120 130 140 150 160 Time (s)

Voltage

Current

Potential

Current

P o te n tia l ( V /S C E )

Bidirectional Transients in Pitting

8E-07 7E-07 6E-07 5E-07 4E-07 3E-07 0 200 400 600 800 Time (secs) 1000 2E-07 1200
C u r r e n t ( A )

-0.378 -0.38

-0.382 -0.384 -0.386 -0.388

Potential Current

P o t e n t ia l ( V / S C E )

Pitting Corrosion
C u rre n t (A )
-1E-06 -1.2E-06 -1.4E-06 -0.03 -1.6E-06 -1.8E-06 800 1000 1200

-0.015 -0.02

-0.025

Voltage Current

-0.035 -0.04 0 200 400 600 Time (s)

Mild steel in 0.01 M NaNO2 + 0.05 M NaCl

P o t e n t ia l ( V / S C E )

Active Corrosion/Hydrogen Evolution

-0.52316 -0.52318 -0.5232 0.000142 0.00014 0.000138 0.000136 0.000134 0.000132 0 0.00013 200 400 600 800 1000 1200 Time (s)

C u rre n t (A )

-0.52314

0.000144

Potential Current

-0.52322 -0.52324 -0.52326

Mild steel in 0.5 wt% HCl

Theoretical Analysis
Several noise generation processes can be modelled as the emission of bursts of charge Shot noise process
pulses of charge q pulses statistically independent pulses infinitely short (may be modified) pulses of constant charge (may be modified)

Shot Noise Analysis

Noise results from random variation in number of pulses arriving within each sample interval Current noise has constant power per unit of bandwidth (white noise)
2 In = 2qIb

where q = charge in pulse I = current b = bandwidth of measuremen t

Shot Noise Analysis

We can estimate the charge in each event from

b I E q= B
Similarly we can estimate the frequency of events from

Icorr B fn = = 2 q b E