1. Technical Field
Embodiments of the invention may relate to a corrosion detector apparatus. Embodiments of the invention may relate to a method of detecting corrosion.
2. Discussion of Art
Some industrial processes may involve the use of a fluid corrosive that can degrade or corrode the equipment used in the processes. Such equipment may include piping, vessels, and heat exchangers. It may be desirable to monitor such degradation or corrosion for maintenance purposes.
General corrosion is widespread and occurs on a relatively large scale or relatively large area. General corrosion is relatively uniform on the surface of a pipe or vessels in the target system, or on a sensor. General corrosion damages and removes metal mass, which changes the geometry, i.e., thickness of the surface, and causes a degradation or depletion of original material. General corrosion compromises the structural rigidity and integrity of a pipe or vessel. Exemplary general corrosion can include, but is not limited to, large-scale surface oxidation, e.g., to form metal oxides. On the other hand, localized corrosion may be widespread or limited to only a few areas of the target system, but is relatively non-uniform and occurs on a relatively small scale. Exemplary localized corrosion can include, but is not limited to, pitting, environmental stress cracking (ESC), (hydrogen) embrittlement, and the like, as well as combinations thereof.
Degradation and corrosion may be estimated using a corrosion coupon. The coupon is exposed to a corrosive environment and periodically monitored. The corrosion rate can be calculated by measuring the weight loss of the coupon due to corrosion. The corroded coupons are examined to determine the type of corrosion.
Another monitoring technique measures the change in electrical resistance of a wire or sensor exposed to the corrosive environment over time. The changing electrical resistance of the wire or sensor indirectly correlates to the corrosion rate of the equipment. Rather than a wire, an electrodes changing polarization resistance is measured in linear polarization resistance (LPR). The changing polarization resistance of the electrode indirectly correlates to the corrosion rate of the equipment.
Another technique is electrochemical noise measurement, which is used in a fluid environment to measure localized corrosion. This technique senses changes in the locale using random bursts of current or potential that may occur during the corrosion process.
It may be desirable to have an apparatus for sensing corrosion that differs from those apparatus currently available. It may be desirable to have a method for sensing corrosion that differs from those methods currently available.
In one embodiment, a corrosion detection apparatus is provided. The corrosion detection apparatus is capable of detecting corrosion on a surface of a pipe or a vessel where the surface contacts a fluid that is corrosive to the surface. The corrosion detection apparatus includes a corrodible element having a contact surface; at least two electrodes that are in electrical communication with each other through a segment of the corrodible element; and a detector in communication with the at least two electrodes. The detector detects a characteristic impedance value from the at least two electrodes through the corrodible element segment.
A method for detecting corrosion is provided in one embodiment. The method includes exposing a surface of a corrodible element segment to a fluid capable of corroding the corrodible element segment, and detecting a characteristic impedance value of the corrodible element segment.
With reference to the drawing figures, like numerals represent substantially the same parts from drawing to drawing.
Embodiments of the invention may relate to a corrosion detector. Embodiments of the invention may relate to a method of detecting corrosion.
As used herein, the term fluid includes liquids, gases and fluidized solids. Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term such as “about” is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
One aspect of the invention relates to a corrosion detection apparatus having the capability of detecting at least two different types of corrosion, when placed within, in contact with, or in proximity to a target system or apparatus for which corrosion detection and/or analysis is desired. The sensor is capable of detecting general corrosion as well as local or localized corrosion. While the target system can be made from any materials, a typical target system includes, but is not limited to metal pipes, vessels, containers, heat exchangers through which a corrosive fluid runs/circulates.
The fluid in the target system may cause damage to the system via chemical means (e.g., corrosion) or mechanical damage (e.g., erosion). In some embodiments, these conditions can include, but are not limited to, increased/decreased pressure, increased/decreased temperature, relatively high/relatively low flow rate, and the like, and combinations thereof. In one embodiment, the corrosive fluid is aqueous. In other embodiments, the corrosive fluid can include a heterogeneous component. Suitable heterogeneous component include solid particles, colloids, or the like. In one embodiment, the corrosive fluid can be a mixture of water, hydrocarbons, and organic solvents. Suitable aqueous fluids may include one or more of waste water, purified water, tap water, an aqueous salt solution such as saline or ocean water, or the like. Suitable hydrocarbons include mixtures or organic compounds. Examples of hydrocarbons include oil and petroleum reactants, and petrochemical intermediates and by-products.
Suitable industrial vessels and pipes are made from metals or metal alloys. Suitable metals include aluminum, copper, chromium, cobalt, iron, nickel, magnesium, tantalum, titanium, tungsten, zinc, and zirconium. Suitable metal alloys include aluminum alloys, copper alloys, iron alloys, nickel alloys, titanium alloys, magnesium alloys, chromium alloys, cobalt alloys, tantalum alloys, tungsten alloys, zinc alloys, and zirconium alloys. Suitable iron alloys may include steels. Tradename alloys suitable for use include HASTALLOY and INCONEL. The pipes and vessels in the target can alternately be made from non-metallic materials or combinations of metallic and non-metallic materials.
In one embodiment, a corrosion detection apparatus includes a sensing element. The sensing element has the same, or a similar, chemical composition to that of the fluid-contacting inner surface of the pipes in the target system to be monitored for corrosion. The sensing element can be made from any of the metals or alloys described above. In one embodiment, the sensing element has a similar surface finish as the fluid-contacting inner surface of the pipes of the target system. By having one or both of the same composition and surface finish, similar corrosive attacks should occur on both the target system and on the sensing element, and the corrosion rate should be about the same.
When a metallic surface of a pipe, a vessel or a sensor is corroded, its sheet resistance or impedance changes as a function of the geometry of the surface as illustrated in
This equation can be generalized to account for the more general circuit impedance via:
Where Rs is the resistance (and Zs is the impedance) across the pre-selected segment; V1 and V2 are the voltage across the same segment; and I is the current through same, as schematically depicted in
or orientation of the electrodes will affect the impedance in a measurable amount. A generalized circuit is shown in
where Z is the impedance, Rs is the circuit resistance, Ls is the circuit inductance, Cs is the circuit capacitance, and ω is the angular frequency.
Simultaneous measurement of general corrosion and localized corrosion on a single sensor can be accomplished with a linear resistive corrosion system, such as the one shown in
When electricity is passed through the corrodible element via the sensor leads, one or more electrical properties can be measured between pairs of electrodes. In one embodiment, the electrical property that is measured is the resistance of each segment described by the above equation, collectively denoted by Ri, where i is an integer in a range of from 1 to (n−1), where n is the number of electrodes arranged on the corrodible element. In other words, for n numbers of electrodes, there are n−1 numbers of the segments whose resistances are measurable.
The pairs of electrodes may be adjacent to one another, but non-adjacent electrodes may also be used to vary spacing or pitch. In other words, spacing or segment size can differ by selecting non-adjacent electrodes for measurements. Examples of such selection include adjacent electrodes, every other electrode, every third electrode, or random electrodes.
For example, the resistance of the corrodible element can be measured by applying a known DC or AC current through the sensor leads and by measuring the resulting voltage across pairs of electrodes. Alternatively, a known DC or AC voltage can be applied to the leads and the current through the segments the corrodible element can be measured. The impedance along the entire the corrodible element, or the sum of all the segments, can be ascertained. Before any corrosion occurs on the corrodible element, the initial resistance Ro should be substantially the same, for any segment on the corrodible element. At a given time t after the corrodible element is immersed in a corrosive fluid, any corrosion that occurs reduces the cross-sectional area of the corrodible element, and increases resistance in the electrode where the corrosion occurred, as discussed further below and shown in
The multiple impedance values of the segments between corresponding pairs of electrodes at any given time, individually denoted as Ri(t), can be used for corrosion analysis or can be compared to the pre-corrosion Ro to get a differential value, ΔRi(t), for corrosion analysis.
Alternately, a reference sensor 1ref (not shown), containing a substantially similar conductive element 10ref (not shown), can be embedded in an insulating substrate isolating the reference sensor from the corrosive environment but exposing it to similar environmental conditions, such as temperature and pressure, as the measuring detection apparatus. This reference sensor 1ref can provide a non-corrosive Rx(t) value for comparison to Ri(t). Rx(t) should is similar to the pre-corrosion Ro, when environmental conditions between the pre-corrosion environment, when Ro is measured and the corrosive environment, when Rx(t) is measured, are similar. Otherwise, the difference between Rx(t) and Ro can be indicative of such conditions, e.g., temperature drift. In this manner, temperature drifts can be corrected for more accurate readings. Alternatively, a thermocouple can be added to the sensor to directly measure the temperature of the sensor.
Either value, ΔRi(t) or Ri(t), for each segment can be plotted on the y-axis of a time-slice histogram or bar graph, for example, with the x-axis representing the position of the segments along the length of the corrodible element. If Ri(t) is used, Ro or Rx(t) may also be plotted as a horizontal line on the histogram for comparison.
General corrosion can be ascertained by at least two methods. General corrosion can be indicated by relatively small differences between Ri(t) and Ro or Rx(t), or by a uniform change between the electrode pairs.
Localized corrosion is indicated by relatively large differences between Rx(t) and Ro or Rx(t), or changes in only specific, discrete electrode pairs. Because resistance is a function of the cross-sectional area of segment 16i between the ith and (i+1)th the electrodes, the presence of localized corrosion between the (i+1)th and the ith electrodes means a smaller cross-sectional area in the particular segment therebetween and thus a higher measured resistance. In other words, localized corrosions can be detected by relatively higher resistance Ri(t) at one or more segments when compared to other Ri(t) values at other segments. On the other hand, general corrosion can be detected by more widespread increase of resistance along a higher number of segments.
Additionally, a single incidence of localized corrosion may significantly reduce the ability of electricity to flow through that localized corrosion, if that local corrosion substantially reduces or cuts through the thickness of the corrodible element. This produces a very strong signal that the corrosion has completely eroded the depth of the electrode.
The dimensions of the corrodible element, such as cross-sectional area, are tailored to the characteristic dimensions of corrosion in the target system as well as the dynamic range of the sensor. An example of this is described above in the graph showing different aspect pitting ratios for different materials. The dimensions may depend upon the specific materials in the target system, the corrosive fluid present during the duration of the corrosion detection/analysis and the type of flow, e.g., laminar or turbulent, in the target system, and the amount of corrosion that is expected. By varying the cross-sectional area of multiple corrodible elements, as in the sensor of
In one embodiment, the segment spacing between the electrodes, and the size and shape of the electrodes are on the order of the dimensions of localized corrosion effect (e.g., the pit diameter), and the dynamic range required or the measurement. The corrosion rates for some industrial systems are shown in
The total number of electrodes electrically connected to the corrodible element can be based on the spacing and on the length L of the corrodible element, or on the absolute size of the corrosion detection apparatus. In general, there is no limit to the number of electrodes that can be deposited on a smart coupon. However, for use in a nominal 1-2″ diameter pipe, using moderate power consumption, and a good statistical sampling of many electrodes to disentangle local and general corrosion, about 16 electrodes should suffice. In other embodiments, the corrosion detection apparatus includes from about 3 to about 20 electrodes, from about 20 to about 50 electrodes, from about 50 to about 100 electrodes, from about 100 to about 200 electrodes, or more than about 200 electrodes.
Referring again to
In another embodiment also illustrated by
Small MEMs sensing elements may be of similar construction to those previously describes or the electrodes may be deployed on a sheet of material. As such the electrodes measure and map the changes in the sheet current, rather than the current flowing in discrete electrodes. This sensor is also known as “RCM on a chip”.
An exemplary deployment of chip as a corrosion detection apparatus is shown in
The surface finish of the sensing element should be similar to that of the metallurgy of the target system. Sensors may be deployed in pairs. A suitably polished sensor similar to that of the target system may be used with another sensor that has the active element that has been slightly abraded. Such a marred or imperfect coupon would tend to corrode or be subject to a corrosive attack on shorter time scales than a nominal coupon, because localized corrosive attacks commence when the protective surface oxide layer(s) is broken and a direct attack on the base metal can be initiated. As such, a nominal sensor, much like a pipe or vessel wall have to have the protective surface layers degraded before a corrosive attack on the base metal can commence. This would under estimate the corrosion rate should there be physical defects in the pipe or vessel due to mechanical such as scratching, marring, or any physical damage during fabrication, transportation, installation, etc. of the vessel or piping. By deploying a marred or imperfect coupon that already has some surface damage where the protective oxide coating is compromised, a more rapid attack can be measured. Therefore, the measurements of this pair of coupons would provide a range of corrosion attacks that may be occurring in the system, including a worst case (i.e. protective oxide films compromised) and a best case (i.e. protective oxide film is not compromised). A reference sensor, described above, can also be deployed with such pair.
Because both the sensor and associated processing electronics are small, the sensor can be embedded into the infrastructure itself. That is, it can be placed into the substrate or wall of the pipe or vessel, and become part of the infrastructure. The sensor can be embedded into a pipe or vessel material without requiring additional machinery to fix it within the pipe or vessel. Replacement pipe sections may be supplied with built-in sensor arrays.
Depending upon the desired electrical properties to be measured and/or analyzed and upon the power supply available, direct current and/or alternating current may be supplied through the sensor leads. Whatever power is supplied through the sensor leads, it may include a (DC) component and/or a variable or periodic (AC) component. Examples of possible power supplied may include, but is not limited to, a sinusoidal voltage/current having a relatively constant maximum amplitude and frequency, a square or ramping wave of voltage/current having a relatively constant maximum amplitude and frequency, a sinusoidal voltage/current having changing frequency/periodicity, a square or ramping wave of voltage/current having changing frequency/periodicity, a sinusoidal voltage/current having changing amplitude, a square or ramping wave of voltage/current having changing amplitude. An electrical source, such as industrial electric power or battery, is used to supply power to sensor leads. The sensor leads may be electrodes or hard wires connected to sensor elements. Other power sources, such as induction coils for creating/focusing magnetic fields and circuits for converting radio frequencies into electric current/voltage, are contemplated for supplying power to sensor leads.
Suitable electrically insulating substrates may include dielectric materials. Suitable dielectric materials may include metal oxides, metal nitrides, metal oxynitrides, or SiLK. Other suitable dielectric materials may include non-electrically-conductive polymer resins. Suitable non-electrically-conductive polymer resins may include epoxy resins, phenolic resins, polyolefins, polysulfones, polyetherimides, polyimides, melamine resins, alkyd thermoset resins. Suitable polyolefins may have a high crystallinity. Suitable high crystallinity polyolefins may include HDPE, i-PP, and the like. Other suitable polyolefins may include partially or completely halogenated poly(alpha-olefin)s. Suitable halogenated poly(alpha-olefin)s may include PVC, PVDC, PVDF, PTFE, FEP, and poly(perfluoroacrylate)s. Thermoplastic materials may be used, too, such as polycarbonates. The electrically insulating polymers may include one or more reinforcing agents. The reinforcing agents may include non-conductive or semi-conducting fibers, permeation/diffusion modifiers, and intercalated clays.
In an alternative embodiment shown in
Another aspect of the invention relates to a method for real-time detection of at least two different types of corrosion (e.g., general corrosion such as surface metal oxidization and localized corrosion such as pitting) using at least one corrosion detection apparatus.
In one embodiment, the inventive method includes the steps of: providing at least one corrosion detection apparatus, which contains one or more corrodible elements, sensor leads, electrodes disposed on the corrodible elements, and an insulating substrate; providing at least one power source for providing power to the sensor; electrically dividing the corrodible elements into segments between pairs of electrodes; and collecting, manipulating, interpreting, monitoring, transmitting, and/or storing data regarding the resistance of the segments to ascertain information relating to the general and local corrosions. This method can provide a real-time corrosion profile.
In addition, capturing/sampling (collection) of various corrosion data either constantly or at repeated/regularly-spaced times/time intervals can yield increased corrosion information about the target system and corrosive fluid environment. Such a corrosion detection system is an improvement compared to having a field engineer manually inspect corrosion coupons and determine weight loss, not more often than once per month.
The embodiments may aid in the collection, monitoring, and/or storage of corrosion data for transmission, manipulation, and/or interpretation remotely from the target system site allows for a determination of corrosion mode without visual inspection; data sampling at arbitrary times, or data sampling at repeated/regularly-spaced times/time intervals offers real-time corrosion information and history, which allows direct correlation of corrosion events with critical target system events (independent or integrated monitoring); and increased capability for measurement accuracy/precision, as what is being measured is the change in one or more electrochemical properties of the conductive sensor element(s) on the substrate, allowing a direct correlation with corrosion behavior; in some cases in the prior art, only the properties of corrosive fluid environment, such as with electrochemical noise (ECN) techniques, only allowing indirect correlation with corrosion behavior.
The foregoing examples are illustrative of some features of the invention. The appended claims are intended to claim the invention as broadly as has been conceived and the examples herein presented are illustrative of selected embodiments from a manifold of all possible embodiments. Accordingly, it is Applicants' intention that the appended claims not limit to the illustrated features of the invention by the choice of examples utilized. As used in the claims, the word “comprises” and its grammatical variants logically also subtend and include phrases of varying and differing extent such as for example, but not limited thereto, “consisting essentially of” and “consisting of.” Where necessary, ranges have been supplied, and those ranges are inclusive of all sub-ranges there between. It is to be expected that variations in these ranges will suggest themselves to a practitioner having ordinary skill in the art and, where not already dedicated to the public, the appended claims should cover those variations. Advances in science and technology may make equivalents and substitutions possible that are not now contemplated by reason of the imprecision of language; these variations should be covered by the appended claims.
This application is a continuation-in-part of U.S. patent application Ser. No. 11/290671, filed on Nov. 30, 2005.
Number | Date | Country | |
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Parent | 11290671 | Nov 2005 | US |
Child | 11685513 | Mar 2007 | US |