GB/T 43666-2024 Corrosion of metals and alloys - Guidelines for corrosion test by electrochemical noise measurements
1 Scope
This document is intended to assist in corrosion testing by electrochemical noise measurement.
It covers test procedures and analysis methods for reliable measurement of electrochemical noise for both uncoated and organically coated metal.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 8044 Corrosion of metals and alloys - Basic terms and definitions
Note: GB/T 10123-2022, Corrosion of metals and alloys - Vocabulary (ISO 8044:2020, IDT)
ISO 17475 Corrosion of metals and alloys - Electrochemical test methods - Guidelines for conducting potentiostatic and potentiodynamic polarization measurements
Note: GB/T 24196-2009, Corrosion of metals and alloys - Electrochemical test methods - Guidelines for conducting potentiostatic and potentiodynamic polarization measurements (ISO 17475:2005, IDT)
3 Terms and definitions
For the purposes of this document, the terms and definitions given in ISO 8044 and the following apply.
3.1
electrochemical noise; EN
fluctuation typically at low frequencies (≤1 HZ) and low amplitude in current and potential generated by electrochemical reactions and other processes on the surface, for example, bubble evolution
3.2
electrochemical potential noise
fluctuation in potential (typically in the range of µV to mV) of an electrode relative to a reference electrode or fluctuation in potential between two similar electrodes
3.3
electrochemical current noise
fluctuation in current (typically in the range of nA to µA) of one electrode or between two electrodes
3.4
electrochemical noise resistance
resistance obtained by dividing the standard deviation of potential noise by the standard deviation of current noise from the time record
3.5
power spectral density of potential
PSDE
power present in the potential noise as a function of frequency
3.6
power spectral density of current
PSDI
power present in the current noise as a function of frequency
3.7
electrochemical noise impedance
Zn
impedance determined as Zn = √(PSD_E/PSD_I ) where all terms are a function of frequency
Note 1: The noise impedance is real and positive.
3.8
working electrode
electronic conductor in contact with the electrolyte, made out of the investigated material
Note 1: This definition differs from that of the same term given in ISO 8044:2015, 6.1.46, “test electrode in an electrochemical cell designed for polarization tests”.
3.9
auxiliary electrode
electrode commonly used in applied polarization to balance the current passing to the working electrode
Note 1: It is usually made from a non-corroding material.
3.10
Nyquist frequency
frequency equal to one half of the sampling frequency (fs/2); maximum frequency about which information can be obtained from the sampled data
3.11
thermal noise
noise resulting from thermal vibrations of electrons and charge carriers
Note 1: Thermal noise is the absolute minimum of the noise that can be expected; also called Johnson noise.
3.12
shot noise
noise due to the quantized nature of the charge carriers that move in very short times causing current peaks
3.13
dummy cell
non-electrochemical cell with a well-defined noise level that usually does not deliberately generate noise above normal thermal noise levels
4 Principles
4.1 The source of EN in corrosion might result from partial faradaic currents, adsorption/desorption processes, surface coverage, and, in the case of localized corrosion, the initiation of pits, crevice corrosion, and mechanical effects from cracking and several other processes. Special care has to be taken as a variety of other sources not related to corrosion might cause fluctuations in current and potential.
4.2 Electrochemical noise can be measured potentiostatically, galvanostatically, or at the free corrosion potential (the various methods are described in Clause 5). Examples of two simple tests with EN measurements on aluminium during pitting corrosion and on organically coated carbon steel can be found in Annexes B and C.
4.3 Electrochemical noise data can be analysed in the time and/or frequency domains. Details of data analysis are described in Annex A.
5 Apparatus and measurement methods
5.1 Instrumentation
5.1.1 Accurate measurement of potential and current requires instruments that have appropriate input impedance (much higher than the system being measured in the case of potential and much lower in the case of current) and sensitivity (sufficient to minimize quantization noise). Suggestions are given in the following Clauses but these will not be sufficient for some systems.
5.1.2 Potential measuring instruments
The instrument should have an input impedance of at least 109 ohm for bare metal and 1011 ohm for coated metal to minimize current drawn from the system during measurement. The higher input impedance might be necessary for very high impedance systems (e.g. for EN measurements with coated metals). The sensitivity and accuracy of the instrument should be sufficient to detect a change of 10 μV or lower for the typical range of 1 V.
5.1.3 Current measuring instruments
The instrument should be capable of measuring current to a resolution of 10−9 A or better with a voltage burden of less than 1 mV. A low voltage burden ammeter is often termed a zero resistance ammeter (ZRA) in corrosion literature.
Note 1: The low voltage burden is only required when the current measurement is made between two corroding working electrodes.
Note 2: The voltage between the terminals, also known as a voltage drop or burden voltage.
5.1.4 Potentiostat
Some measurement configurations use a potentiostat to control the potential of an electrode. The potentiostat shall have low noise characteristics, which should be tested by using a dummy cell with comparable properties to the system under investigation (see Clause 8 or Reference [1]).
5.1.5 Galvanostat
Some measurement configurations use a galvanostat to apply a current to an electrode. The galvanostat shall have low noise characteristics, which should be tested by using a dummy cell with comparable properties to the system under investigation (see Clause 8 or Reference [1]).
5.1.6 Grounding, shielding, and isolation
It is very important to ensure correct grounding and shielding of the measurement system. In particular, there should be a single well-defined connection to ground in order to avoid ground loops and to minimize induced interference. Isolated or differential measuring devices will commonly be required to avoid short-circuit connections to ground and ground loops, especially in plant monitoring conditions.
5.2 Measurement configurations
Schematics of the most important EN measurement configurations can be seen in Figure 1.
a) Potentiostatic current noise
b) Galvanostatic potential noise
c) Open-circuit potential noise
d) Current noise at open-circuit potential
e) Simultaneous current and potential noise
Key
1——potentiostat (see 5.1.4)
2——current measurement device (see 5.1.3, implies connection to PC or other device for recording or analysis)
3——working electrode (WE)
4——reference electrode (RE)
5 auxiliary electrode (AE)
6——galvanostat (see 5.1.5)
7——potential measurement device (see 5.1.2, implies connection to PC or other device for recording or analysis)
Figure 1 - Configurations for measurements
Standard
GB/T 43666-2024 Corrosion of metals and alloys-Guidelines for corrosion test by electrochemical noise measurements (English Version)
Standard No.
GB/T 43666-2024
Status
valid
Language
English
File Format
PDF
Word Count
10000 words
Price(USD)
300.0
Implemented on
2024-10-1
Delivery
via email in 1~3 business day
Detail of GB/T 43666-2024
Standard No.
GB/T 43666-2024
English Name
Corrosion of metals and alloys-Guidelines for corrosion test by electrochemical noise measurements
GB/T 43666-2024 Corrosion of metals and alloys - Guidelines for corrosion test by electrochemical noise measurements
1 Scope
This document is intended to assist in corrosion testing by electrochemical noise measurement.
It covers test procedures and analysis methods for reliable measurement of electrochemical noise for both uncoated and organically coated metal.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 8044 Corrosion of metals and alloys - Basic terms and definitions
Note: GB/T 10123-2022, Corrosion of metals and alloys - Vocabulary (ISO 8044:2020, IDT)
ISO 17475 Corrosion of metals and alloys - Electrochemical test methods - Guidelines for conducting potentiostatic and potentiodynamic polarization measurements
Note: GB/T 24196-2009, Corrosion of metals and alloys - Electrochemical test methods - Guidelines for conducting potentiostatic and potentiodynamic polarization measurements (ISO 17475:2005, IDT)
3 Terms and definitions
For the purposes of this document, the terms and definitions given in ISO 8044 and the following apply.
3.1
electrochemical noise; EN
fluctuation typically at low frequencies (≤1 HZ) and low amplitude in current and potential generated by electrochemical reactions and other processes on the surface, for example, bubble evolution
3.2
electrochemical potential noise
fluctuation in potential (typically in the range of µV to mV) of an electrode relative to a reference electrode or fluctuation in potential between two similar electrodes
3.3
electrochemical current noise
fluctuation in current (typically in the range of nA to µA) of one electrode or between two electrodes
3.4
electrochemical noise resistance
resistance obtained by dividing the standard deviation of potential noise by the standard deviation of current noise from the time record
3.5
power spectral density of potential
PSDE
power present in the potential noise as a function of frequency
3.6
power spectral density of current
PSDI
power present in the current noise as a function of frequency
3.7
electrochemical noise impedance
Zn
impedance determined as Zn = √(PSD_E/PSD_I ) where all terms are a function of frequency
Note 1: The noise impedance is real and positive.
3.8
working electrode
electronic conductor in contact with the electrolyte, made out of the investigated material
Note 1: This definition differs from that of the same term given in ISO 8044:2015, 6.1.46, “test electrode in an electrochemical cell designed for polarization tests”.
3.9
auxiliary electrode
electrode commonly used in applied polarization to balance the current passing to the working electrode
Note 1: It is usually made from a non-corroding material.
3.10
Nyquist frequency
frequency equal to one half of the sampling frequency (fs/2); maximum frequency about which information can be obtained from the sampled data
3.11
thermal noise
noise resulting from thermal vibrations of electrons and charge carriers
Note 1: Thermal noise is the absolute minimum of the noise that can be expected; also called Johnson noise.
3.12
shot noise
noise due to the quantized nature of the charge carriers that move in very short times causing current peaks
3.13
dummy cell
non-electrochemical cell with a well-defined noise level that usually does not deliberately generate noise above normal thermal noise levels
4 Principles
4.1 The source of EN in corrosion might result from partial faradaic currents, adsorption/desorption processes, surface coverage, and, in the case of localized corrosion, the initiation of pits, crevice corrosion, and mechanical effects from cracking and several other processes. Special care has to be taken as a variety of other sources not related to corrosion might cause fluctuations in current and potential.
4.2 Electrochemical noise can be measured potentiostatically, galvanostatically, or at the free corrosion potential (the various methods are described in Clause 5). Examples of two simple tests with EN measurements on aluminium during pitting corrosion and on organically coated carbon steel can be found in Annexes B and C.
4.3 Electrochemical noise data can be analysed in the time and/or frequency domains. Details of data analysis are described in Annex A.
5 Apparatus and measurement methods
5.1 Instrumentation
5.1.1 Accurate measurement of potential and current requires instruments that have appropriate input impedance (much higher than the system being measured in the case of potential and much lower in the case of current) and sensitivity (sufficient to minimize quantization noise). Suggestions are given in the following Clauses but these will not be sufficient for some systems.
5.1.2 Potential measuring instruments
The instrument should have an input impedance of at least 109 ohm for bare metal and 1011 ohm for coated metal to minimize current drawn from the system during measurement. The higher input impedance might be necessary for very high impedance systems (e.g. for EN measurements with coated metals). The sensitivity and accuracy of the instrument should be sufficient to detect a change of 10 μV or lower for the typical range of 1 V.
5.1.3 Current measuring instruments
The instrument should be capable of measuring current to a resolution of 10−9 A or better with a voltage burden of less than 1 mV. A low voltage burden ammeter is often termed a zero resistance ammeter (ZRA) in corrosion literature.
Note 1: The low voltage burden is only required when the current measurement is made between two corroding working electrodes.
Note 2: The voltage between the terminals, also known as a voltage drop or burden voltage.
5.1.4 Potentiostat
Some measurement configurations use a potentiostat to control the potential of an electrode. The potentiostat shall have low noise characteristics, which should be tested by using a dummy cell with comparable properties to the system under investigation (see Clause 8 or Reference [1]).
5.1.5 Galvanostat
Some measurement configurations use a galvanostat to apply a current to an electrode. The galvanostat shall have low noise characteristics, which should be tested by using a dummy cell with comparable properties to the system under investigation (see Clause 8 or Reference [1]).
5.1.6 Grounding, shielding, and isolation
It is very important to ensure correct grounding and shielding of the measurement system. In particular, there should be a single well-defined connection to ground in order to avoid ground loops and to minimize induced interference. Isolated or differential measuring devices will commonly be required to avoid short-circuit connections to ground and ground loops, especially in plant monitoring conditions.
5.2 Measurement configurations
Schematics of the most important EN measurement configurations can be seen in Figure 1.
a) Potentiostatic current noise
b) Galvanostatic potential noise
c) Open-circuit potential noise
d) Current noise at open-circuit potential
e) Simultaneous current and potential noise
Key
1——potentiostat (see 5.1.4)
2——current measurement device (see 5.1.3, implies connection to PC or other device for recording or analysis)
3——working electrode (WE)
4——reference electrode (RE)
5 auxiliary electrode (AE)
6——galvanostat (see 5.1.5)
7——potential measurement device (see 5.1.2, implies connection to PC or other device for recording or analysis)
Figure 1 - Configurations for measurements