Electricity: measuring and testing – Impedance – admittance or other quantities representative of... – Lumped type parameters
Reexamination Certificate
2002-03-26
2004-01-27
Deb, Anjan K. (Department: 2858)
Electricity: measuring and testing
Impedance, admittance or other quantities representative of...
Lumped type parameters
C324S696000, C324S713000, C204S404000, C205S775500
Reexamination Certificate
active
06683463
ABSTRACT:
TECHNICAL FIELD OF THE INVENTION
This invention relates to sensors for detecting corrosion in metals, and more particularly to a sensor having an array of electrochemical cells for localized corrosion detection.
BACKGROUND OF THE INVENTION
Corrosion is a natural process that involves a metal atom M being oxidized, whereby it loses one or more electrons and leaves the bulk metal, M→M
m+
+me
−
. The lost electrons are conducted through the bulk metal to another site where they reduce (i.e. combine with) a reducible species such as a dissolved gas or a positively charged ion G
+
that is in contact with the bulk metal, N+ne
31
→N
n−
and G
m+
+me
−
→G.
In corrosion parlance, the site where metal atoms lose electrons is called the anode, and the site where electrons are transferred to the reducible species is called the cathode. These sites can be located close to each other on the metal's surface, or far apart depending on the circumstances. When the anodic and cathodic sites are continuous, the corrosion is more or less uniform across the surface. When these sites are far apart, the anodic sites corrode locally.
A corrosion path is essentially an electric circuit, since there is a flow of current between the cathode and anode sites. In order for a current to flow, Kirchoff's circuit laws require that a circuit be closed and that there exists a driving potential (or voltage). Part of the corrosion circuit is the base metal itself; the rest of the circuit exists in an external conductive solution (i.e. an electrolyte) that must be in contact with the metal. This electrolyte serves to take away the oxidized metal ions from the anode and provide reduction species (either nonmetalic atoms or metallic ions) to the cathode. Both the cathode and anode sites are immersed in an electrolyte for the corrosion circuit to be complete.
In corroding systems, potential gradients can be created by a number of mechanisms. These include differences in the free energy or the related electrochemical potentials for different reactions and gradients in the concentration of charged species in the solution. When two electrodes exhibiting differing potentials are electrically connected, a current flows in the external circuit.
There are various approaches to monitoring corrosion; electrochemical approaches rely on the above-described electrochemical corrosion principles and the measurement of potentials or currents to monitor corrosion damage.
One approach to monitoring corrosion is an electrical noise method, which uses electrodes to detect electrochemical noise due to localized corrosion. This method has been implemented using a single pair of near identical large electrodes, and measuring the current noise between the two electrodes. With two large electrodes, each may have a number of anodic areas and a number of cathodic areas, resulting the possibility of zero current flows between the two electrodes. In general, the overall current noise is not well suited to indicating corrosion rate at a particular site of the metal.
U.S. Pat. No. 6,132,593 to Tan, entitled “Method and Apparatus for Measuring Localized Corrosion and Other Heterogeneous Electrochemical Processes”, describes a multi-sensor electrode, comprising a number of wire beams. This multi-sensor electrode simulates a conventional one-piece electrode surface. Measurements are made by inserting a zero-resistance ammeter between a terminal of a selected wire and the coupled terminals of all other wires. Multiple measurements provide a current distribution map of electrochemical responses on the contact surface of the electrode.
When it is not practical to directly test the component of interest itself, separate sensors can be installed in the same environment. These sensors test a sample of the same material as the component of interest and can be removed from the main component structure and examined in detail. The use of such sensors facilitates the measurement of corrosion damage in a well-controlled manner over a finite sensor area.
SUMMARY OF THE INVENTION
One aspect of the invention is an electrochemical corrosion sensor that provides multiple channels of voltage output signals to a high impedance voltmeter. In one embodiment, the sensor has an insulating base. An array of metallic electrodes is arranged within the base, and the electrodes are supported within the base such that each electrode has a small area exposed on one surface of the base and such that each electrode is electrically insulated from other electrodes within the base. A common electrical lead connects each electrode to the voltmeter. A second electrical lead associated with each electrode connects the electrode to the voltmeter across a resistor associated with the electrode. The electrical connections provide a voltage measurement for each electrode across the resistor associated with that electrode.
In another embodiment, the sensor has a base that is identical in metallurgical characteristics to the equipment or part of interest. Each electrode is mounted on this base such that it is electrically insulated from the base. Additional embodiments of the invention are described herein.
An advantage of the invention is that the sensor simulates a bulk metal undergoing corrosion. It is useful for monitoring localized corrosion of metallic materials in various industries, such as the chemical, oil and gas, and power generation industries. It may be used for both field and laboratory applications.
The use of multiple resistors allows use of a voltmeter to measure the current. The measurement of currents using the multiple resistors with each of them being permanently connected to one of the electrodes eliminates the need for connection and disconnection of the current circuit between each electrode and a common joint. The measurement of the current from each electrode only involves the on/off connections of the voltmeter terminals between the resistors. Therefore, the sensor of the present invention does not perturb the corrosion process during the measurement and provides accurate measurement of the corrosion current taking place at each electrode.
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patent: 6132593 (2000-10-01), Tan
Unni Steismo et al. “Aspects of testing and selecting stainless steels for sea water applications” 1994, Paper # 492, Corrosion 94, Annual Conference and Corrosion show Sponsored by NACE International.*
International Preliminary Examining Authority PCT/US02/09608, Nov, 15, 2002.
Sikora, J., et al.; “Analysis Current and Potential Oscillations on 304 SS During Metalstable Pitting”, Proceedings of the Symposium on Critical Factors in Localized Corrosion III; The Electrochemical Society, Inc. Pennington, NJ; pp. 508518, 1999.
Lumsden, J.B., et al.; “Electrochemical Noise for Carbon Steel in Sodium Chloride Solutions—Effect of Chloride and Oxygen Activity”, Corrosion 92, Paper No. 224, The NACE Annual Conference, Houston, TX., 1992.
Rothwell, A.N., et al.; “Electrochemical Noise Techniques for Determining Corrosion Rates and Mechanisms”, Corrosion 92, Paper No. 223, The NACE Annual Conference, Houston, TX., 1992
Qingdong, Z.; “A Novel Electrochemical Testing Method and Its Use in the Investigation of Underfilm Corrosion of Temporary Protective Oil Coating”, Corrosion, vol. 56, No. 7; pp. 722-726., 2000.
Rogne, T., et al.; “Aspects of Testing and Selecting Stainless Steels for Sea Water Applications”, The Annual Conference and Corrosion Show Sponsored by NACE International; Paper No. 492., 1994.
Sridhar Narasi
Yang Lietai
Baker & Botts L.L.P.
Deb Anjan K.
Southwest Research Institute
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