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By Carl E. Jaske, John A. Beavers, and Neil G. Thompson CC Technologies, Dublin, OH
Fourth International Conference on Process Plant Reliability
Marriott Westside Hotel Houston, Texas November 15-17, 1995
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and heat exchangers. Copyright © 1995 by Gulf Publishing Company and the authors. valves. Established technologies include measuring environmental conditions. whereas internal attack is caused by fluids being transported. or processed. such as piping. vessels. piping. Emerging technologies include the use of advanced electrochemical testing techniques and the application of specialized probes for stress-corrosion cracking and pitting corrosion. especially for vessels. Examples that illustrate the use of both established and emerging corrosion monitoring technologies are presented and discussed.1-5 Corrosion monitoring is an essential element of these programs and is used to assess the deterioration of structural and mechanical components. stored. exposing material coupons. linear polarization resistance. Corrosion attack is the most serious aging mechanism for such equipment. advantages. This document may not be reproduced in any manner without permission from the copyright owners. the effects of corrosion must be incorporated into component remaining life assessment and aging management programs. In a general corrosion assessment. the possibility of both external and internal attack must be considered.8 Proceedings of the 1995 Process Plant Reliability Conference. Typically. . valves.Improving Plant Reliability Through Corrosion Monitoring Abstract Corrosion is major problem in petroleum refineries and chemical process plants. External attack is caused by the corrosive species in the ambient environment. This information then can be used to alter operating conditions to reduce corrosion or to plan maintenance and repair work. All rights reserved. condensers. Corrosion can limit the safe and useful life of process equipment. and disadvantages of both established and emerging technologies for corrosion monitoring. Corrosion can cause either a penetration of the fluid containment boundary that results in leak or a decrease in structural strength that results in a component failure. and using electrical resistance. For the safe and reliable operation of these components. This paper reviews the features. Thus. vessel internals. the materials from which it is made are subject to aging. indications of corrosion are found by means of inspections conducted during planned shutdowns and preventative maintenance. Key equipment. As this equipment grows older. can be degraded by corrosion attack. Corrosion attack of process equipment may be external or internal. it is important to detect and quantify the amount of corrosion that occurs. lead to unexpected failures and shutdowns. boilers.7.6 Corrosion monitoring also can provide significant benefits when it is integrated into process control. and pressure-boundary components that contain hazardous fluids. often 10 years or more. Corrosion monitoring during operation can help minimize such damage by indicating when corrosion initiated and by measuring the rate of corrosion damage. and galvanic probes. If corrosion has been unexpectedly severe or if inspections have been infrequent. Such attack can reduce equipment performance and reliability and. Introduction Much of the key equipment used in petroleum refineries and chemical process plants has been in service for a long time. in extreme cases. equipment damage can occur.
which is the focus of the remaining discussion. Periodic assessment is the most common and widely used method of corrosion monitoring. they are considered to be continuous. The main reasons for performing periodic monitoring are (1) to evaluate materials performance under service conditions. Summary of Corrosion Monitoring Techniques. and temperature are commonly measured for this purpose. (3) to evaluate and control the production process. electrochemical potential. The . The primary purpose of this paper is to review direct measurement techniques. Table 1 summarizes the primary corrosion monitoring techniques in these two categories. and other industries have begun to use corrosion monitoring to evaluate the performance and reliable life of equipment. Table 1. The indirect techniques use parameters that indicate the presence or absence of corrosion and/or the degree of corrosion in specific material/environment system. when measurements can be made in a relatively short time interval with respect to process fluctuations. Continuous monitoring techniques also can be applied periodically. (2) to continuously evaluate materials performance. the oil and gas industry has employed corrosion monitoring more than other industries9-13. The chemical process industry also has used corrosion monitoring methods for a number of years14. November 15-17. (2) to aid in materials selection. as is indicated in Table 1.16 Corrosion monitoring techniques can be divided into (1) methods that indirectly measure parameters related to corrosion and then infer corrosion behavior from some model of the corrosion process and (2) methods that directly measure corrosion behavior. The main reasons for performing continuous monitoring are (1) to provide integrated process control. 1995 Background Corrosion monitoring has been utilized for many years and has evolved into a relatively sophisticated field of technology.4 Fourth International Conference on Process Plant Reliability. Direct Measurement Nondestructive Inspection (NDI) Material Test Coupons Cyclic Potentiodynamic Polarization (CPP) Electrical Resistance (ER) Probes Linear Polarization Resistance (LPR)* Galvanic Currents (GC)* Electrochemical Impedance Spectroscopy (EIS)* Electrochemical Noise (EN)* * Capable of continuous monitoring. In the past. There is always some time interval required to collect and analyze the data that are used for calculation of the corrosion rate. However. pH.15. For example. No direct measure of corrosion rate is truly continuous. Indirect Measurement Biological Counts Potential* Hydrogen* Specific Ions* pH* Temperature* Conductivity* The asterisks in Table 1 indicate techniques that can be used to continuously monitor corrosion. and (4) to provide information for life assessment. whereas the other techniques are applicable to only periodic monitoring. and (3) to measure parameters used in on-line life assessment.
and galvaniccurrent (GC) measurement are well established techniques for corrosion monitoring. examined for evidence of localized corrosion attack such as pitting or cracking. calipers. and cannot be used to inspect welds. electrical resistance (ER). However. UT can be employed to inspect regions near welds.Improving Plant Reliability Through Corrosion Monitoring 5 emphasis of this paper is on continuous monitoring techniques. ultrasonic testing (UT). the coupons are removed from the environment. but coverage of large areas requires much longer inspection times with UT than with MFL. MFL is used to inspect storage tanks and underground pipelines. Calipers and depth gauges also find limited application. Magnetic flux leakage (MFL). UT is applicable to all structural metals and alloys. UT is typically more sensitive than MFL. Trends in the amount of wall loss and the general corrosion rate can be established from measurements taken at the same location at various times in the operating history of a component. and depth gauges are used to measure wall thickness. MFL can be applied only to ferrous materials. and modern. material coupon exposures. Established Corrosion Monitoring Methods Nondestructive inspection (NDI). CR. proper transducers. cyclic potentiodynamic polarization (CPP). The corrosion rate. (µm/year) is then determined using the following relationship: CR = 10. Nondestructive Inspection (NDI) NDI is the most widely used method of periodic corrosion monitoring. Each of these techniques is discussed separately in the following sub-sections of this paper. linear polarization resistance (LPR). UT is widely used to measure wall thickness and to detect and characterize cracks. economic means of detecting and characterizing areas of significant wall loss. Material Coupon Exposures Unstressed material coupons are often exposed to the operating environment to periodically evaluate corrosion behavior. After some planned exposure time. MFL can cover large areas in a relatively short time and provides a rapid. For example. They can be used to measure wall thickness or depth of corrosion attack only when there is sufficient access to the area that is to be inspected. computerized instrumentation.000 WL DAt (1) . With appropriate calibration standards. and weighed to determine the amount of material lost during the exposure period. radiography. Radiography is used in certain limited cases to measure wall thickness and detect cracks. Techniques that are restricted to periodic monitoring will be discussed only briefly. is not as sensitive to local variations in wall thickness as other methods.
Cyclic Potentiodynamic Polarization (CPP) To a limited extent. Its general applicability and relatively low cost make the ER technique quite popular for general industrial use. which makes CPP testing a periodic corrosion monitoring technique.18-24 Gareau23 illustrated the use of a computerized system for data transmission from several remote sites to a central control facility. ER is a periodic corrosion monitoring technique. is given by the following expression: L R = ρ A (2) where ρ is the resistivity of the probe material. including environments consisting of poor or non-continuous electrolytes. A wide variety of probe configurations are commercially available. For field use. Details of the CPP technique are given in ASTM–G-61. November 15-17. Corrosion causes a reduction of A. If localized attack is observed. L is the probe length. The industrial use of ER monitoring is quite varied. the CPP probe typically must be replaced after each test. a metal sample is immersed in an actual or simulated electrolyte. CPP is an accelerated. such as vapors. gases. Stressed specimens are sometimes exposed to the operating environment to assess a material’s susceptibility to stress-corrosion cracking. and non-aqueous liquids. the electrochemical potential is scanned with respect to a reference electrode. and the ensuing current is measured. A is the exposed surface area of the coupon (cm2).17 However.6 Fourth International Conference on Process Plant Reliability. oil field equipment. 1995 where WL is the coupon weight loss (g). Wedge-opening-loading (WOL) type compact tension specimens are used to measure stresscorrosion-crack growth behavior and to evaluate the threshold stress intensity factor for stresscorrosion cracking. These can be applied to most corrosion monitoring applications in the process industry. Example applications include fluidized bed combustors. Electrical Resistance (ER) The ER method can be applied to a broad range of corrosion conditions. R. CPP tests have been used in the field. Practical ER probe designs include an embedded reference element that does not corrode. which is accompanied by a corresponding proportional increase in R. Pre-stressed U-bend specimens or bolt-loaded threepoint bending specimens are used to evaluate stress-corrosion-crack initiation resistance. the depth of attack is obtained from surface measurements or from measurements on metallographic sections through the coupon. the ER data were . The reference element is used to compensate for temperature variations since it is maintained at the same temperature as the exposed element. This method is based upon the simple measurement of the electrical resistance of a metal probe (or element) exposed to the service environment. and t is the exposure time (year). Since a fairly long time is usually required to produce a significant change in R. based on Equation (2). components exposed to the atmosphere. CPP is an electrochemical technique that is primarily used in the laboratory to evaluate the possibility for initiation of pitting and crevice corrosion. destructive testing technique. and A is the probe crosssectional area. The probe resistance. “wet” hydrocarbons. At this central facility. D is the material density (g/cm3).7. and chemical process equipment. With this technique.
These results point out that the ER technique is sensitive to pitting attack and provides a rate that is some intermediate value between the general corrosion rate and the penetration rate. et al. However. Thierry. and linear polarization resistance (LPR) measurements (see next sub-section of this paper) in cooling water systems. and analyzed to obtain information on corrosion at the remote sites. et al. Analog Circuit for a Single Time Constant Corroding Interface. When a DC or low-frequency AC corrosion rate measurement is made. Reference Electrode Rs C Rp Substrate Solution Interface Rs = Uncompensated Resistance Rp = Polarization Resistance C = Capacitance Figure 1. Thierry.25 compared the results of weight-loss-coupon exposures. whereas the ER technique took several days to detect these changes in corrosivity. Figure 1 schematically illustrates an analog electrical circuit for a simple corroding fluid/metal interface. The resistivity of many aqueous environments is relatively low. Rs and Rp are two resistors in series. ER measurements. Rp must be measured separately from Rs to avoid errors in calculating the corrosion rate. Stern and Geary26 showed that the relationship between Rp and corrosion rate was well approximated by the following equation: . and concrete. the exact relationship between the measured rate and the actual rates is unknown. Linear Polarization Resistance (LPR) LPR is the most common continuous monitoring technique employed to determine corrosion rate. They concluded that the ER measurements indicated corrosion rates greater than those observed on the coupons when there was significant localized corrosion of the coupons. The polarization resistance (Rp) is related to the corro sion rate. soils. The solution resistance (Rs) is the resistance between the corroding interface and the reference electrode used to perform the electrochemical measurement. atmospheric environments.Improving Plant Reliability Through Corrosion Monitoring 7 monitored in real time. In these cases. manipulated. This result experimentally confirms that ER is a periodic corrosion monitoring technique. For small changes (±20 mV) from the free-corrosion potential. in some aqueous environments.25 also found that the LPR technique could detect sudden changes in the corrosivity of the water within a few hours. However. Rs is often negligible compared with Rp and can be ignored in calculating the corrosion rate.
Figure 2 shows an example of such LPR data. shows that Rp is the slope of the linear E versus I relationship near the free-corrosion potential. it follows that I cor = C Rp (5) The corrosion rate (CR) can be computed from Icor using the following equation: I M CR = cor FZD (6) where M is the molecular weight of the metal. and D is the metal’s density. If a proportionality constant.3 (β a + β c ) (4) then. . 1995 Rp = βa βc ∆E = ∆I 2.3 I cor (β a + β c ) (3) where ∆E is the change in corrosion potential. Equation (3). the potential is varied 20 mV or less above and below the freecorrosion potential and the corresponding current is measured. and β c is the cathodic Tafel slope. known as the Stern-Geary equation. from Equation (3). β a is the anodic Tafel slope. Typical Potentiodynamic Linear Polarization Resistance (LPR) Data. November 15-17. β a is the anodic Tafel slope. To apply the LPR technique. The plotted symbols connected by the light line represent the actual measured data. is defined as C= βa βc 2. automated instrumentation is used to obtain the data and compute Rp. C. F is Faraday’s constant. In typical applications of the LPR technique. while the heavy line represents the best linear fit of the data. Z is the metal’s valence. mV E cor ∆ E/ ∆ I = R p -20 0 Current Figure 2. and a correction is made for the value of Rs in high resistivity environments. The slope of this line is the value of Rp. ∆I is the change in corrosion current. The Tafel slopes are estimated as the magnitude of the change in potential per decade of current as the potential is shifted away from the free-corrosion potential in the anodic or cathodic direction. while β c is the cathodic Tafel slope.27 +20 Data Change in Potential. Icor is the corrosion current density.8 Fourth International Conference on Process Plant Reliability.
One or both of the following two types of transient measurements are normally made: (1) the potential noise between two identical electrodes and/or (2) the current noise between two identical electrodes coupled through a zero-resistance ammeter. the amount of metal loss. whereas unstable or stable pitting generate random events of short duration or individual events of longer duration. Each of these techniques is discussed separately in the following sub-sections of this paper.50-51 stress-corrosion cracking.35-36 chemical process plants.38 pulp and paper plants. Like other electrochemical methods. Emerging Corrosion Monitoring Methods Electrochemical noise (EN). and possibly stress-corrosion cracking. In recent years. and special-purpose probes are emerging techniques for corrosion monitoring. special probes have been developed for high-resistivity and atmospheric environments.34 pipelines.50-54 and corrosion of coated metals. the use of LPR measurements was limited to aqueous solutions with low resistivities. This current is then correlated with the corrosion rate of the more active of the two metals in the probe. respectively. which is related to the previously described Rp value.37.39 and water treatment equipment. whereas the flush configuration has three concentric elements that are mounted flush with the wall of the equipment. The measured data are analyzed to provide information on the type of corrosion.31 Figure 3 illustrates typical commercially available LPR probe configurations. typically in the range of 10-3 to 1 Hz.56 The EN technique is considered to provide continuous monitoring for practical applications. The triangular and linear configurations have three elements that protrude into the environment. Increased levels of dissolved oxygen in the water greatly increase the galvanic currents and are correlated with corrosion rates. crevice corrosion. electrochemical impedance spectroscopy (EIS). Metal loss is estimated employing a noise resistance value.55. that are produced by the corrosion process. Electrochemical Noise (EN) Several investigators43-49 have reviewed the application of EN measurement to corrosion monitoring. This technique utilizes measurements of transient electrochemical events.32. and in some cases. In the past.40 Galvanic-Current (GC) Measurement Galvanic-current measurements are used to monitor corrosion rates in cooling water systems. Applications of LPR include oil-field equipment. A major of advantage of the EN technique is its ability to provide information on localized corrosion — pitting. EN monitoring also has been applied to general corrosion. EN is sensitive to pitting corrosion because passive conditions typically generate low noise. and the galvanic current between them is measured using a zero-resistance ammeter. The galvanic probe contains elements of two dissimilar metals.28-30.Improving Plant Reliability Through Corrosion Monitoring 9 The LPR technique is widely used by industry to continuously monitor corrosion rates. and the use of atmospheric LPR probes has become commonplace. EN results are based on analysis of data collected over .42 GC measurements are used to monitor water injection systems or other water-system equipment where oxygen leaking into the water can markedly increase the corrosion rates of steel components.41. the initiation of localized corrosion.
. 1995 Triangular Configuration Linear Configuration Flush Configuration Figure 3.10 Fourth International Conference on Process Plant Reliability. Illustration of Typical Linear Polarization Resistance (LPR) Probes. November 15-17.
the high-frequency impedance represents Rs and the low-frequency impedance represents Rp + Rs. as does LPR. (2) sophisticated analysis and expert interpretation of the data. Typical Bode Plot Produced by EIS Measurements. . LPR determines only Rp. The industrial use of EN monitoring should increase as these limitations are overcome by future developments. Electrochemical Impedance Spectroscopy (EIS) EIS is a continuous corrosion monitoring method similar to LPR. Impedance. in that both yield the value of Rp + Rs. Impedance is then calculated by dividing the applied potential by the corresponding measured current.Improving Plant Reliability Through Corrosion Monitoring 11 some time period ranging up to several minutes. EIS measures the same Rp value as LPR method. The value of Rp is calculated by subtracting the high-frequency impedance from the low-frequency impedance. The current waveform is measured for each applied potential waveform. and (3) minimization or filtering of background electrical noise that can mask EN in the field. Ohm Rp + R s Rs 10 -4 10 -2 10 0 10 2 10 4 10 6 Frequency. Instead of employing a DC potential. Assuming a single time constant circuit analog model (Figure 1). Hz Figure 4. as well as providing mechanistic information. EIS has little advantage over LPR as a continuous corrosion monitoring technique. and a Bode plot of the logarithm of impedance as a function of the logarithm of frequency is prepared as shown in Figure 4. Limitations of this method are that it requires (1) relatively expensive equipment. EIS is typically implemented by applying a series of sinusoidal potential fluctuations at amplitudes of ±10 to 15 mV about the free-corrosion potential and at frequencies in the range of 10-3 Hz to 20 kHz. and that value is related to corrosion rate by Equations (3) through (6). The low-frequency EIS measurement is equivalent to the LPR measurement. EIS employs a variable-frequency AC excitation potential.. If the Rs value is not significant or if the LPR instrumentation corrects for the Rs error. whereas EIS determines both Rp and Rs.
direct techniques for monitoring localized corrosion. In contrast. Additional periodic corrosion data can be obtained by use of material coupon exposures and ER probes. continuous monitoring allows corrosion conditions to be measured in real time. The applied pressure is adjusted to provide the desired stress in the tube wall and monitored to indicate when failure occurs. a sensitized stainless steel probe can be used to simulate worst-case conditions for a stainless steel vessel. Established methods that monitor general corrosion continue to be improved and refined. These stresscorrosion cracking probes show promise and currently are being evaluated by means of both laboratory and field testing. Emerging techniques. Discussion and Summary Corrosion monitoring instrumentation and methodologies are becoming more sophisticated and reliable. The tube material is selected to simulate that used in the equipment that is being monitored.015). such as pitting and stress-corrosion cracking.65 underwater pipelines. The internal pressure within the probe can be varied to accelerate or decelerate the rate of attack and to give a means of discriminating among the mechanisms of attack.57-60 EIS techniques are not generally used in industrial corrosion rate monitoring systems because of the higher equipment cost and increased data analysis required by EIS compared with LPR. The EN technique is capable of indicating the initiation of localized corrosion but generally does not provide corrosion-rate information. Nondestructive inspection for corrosion attack should be included in all equipment reliability management and maintenance programs. However. Emerging methods for monitoring localized corrosion are being developed and field testing. but there is a chance for significant corrosion attack to occur between measurements.61 reinforcing steel in concrete.67 and organic coatings on metal.62. Special probes for . such as EN and EIS.63 high-temperature equipment. Techniques such as ER and LPR measure average properties and are inherently insensitive to localized phenomenon. there is considerable interest in developing simple. Both periodic and continuous monitoring techniques are available for industrial application. Periodic techniques are relatively inexpensive and fairly easy to incorporate into plant maintenance programs. Because of the shortcomings of the current techniques. The LPR technique can be employed to continuously monitor general corrosion behavior. November 15-17.69 Special-Purpose Probes Most of the commercial techniques for corrosion monitoring described above measure rates of general corrosion and are relatively insensitive to localized forms of corrosion. The general applicability of EN to monitoring stress-corrosion cracking also has not been established.28. the probe material can be modified to provide an acceleration of the localized corrosion attack. 1995 Several reviews of corrosion monitoring techniques include discussions of EIS.68. The probe consists of a pressurized tube that is inserted into the process stream or operating environment. so sudden changes in corrosion conditions can be detected and dealt with in a timely fashion.12 Fourth International Conference on Process Plant Reliability.66 sour gas equipment. CC Technologies recently applied for a patent on a probe for monitoring stress-corrosion cracking (Application Number 08/418. Periodic monitoring can provide valuable information on long-term trends in material degradation. EIS has been used to periodically assess corrosion rates for many industrial components. Alternatively.64. can provide information on localized corrosion and corrosion mechanisms. For example.
Aging and Life Extension of Major Light Water Reactor Components. Continuous monitoring techniques do provide rapid feedback on changes in the environment or manufacturing process. new monitoring methods for sensing localized corrosion are emerging. V. Important parameters to measure include potential. the monitoring methods have been widely applied to general corrosion problems. The computer system then can compute estimates of corrosion behavior in real time. 2. Systematic procedures for corrosion monitoring provide a cost-effective means of improving the reliability of important components and equipment that are potentially subject to degradation from corrosion. 1993. and readily applicable to process-plant equipment. Historically. The results of such monitoring can then be used to modify proposed operational changes or to employ alternate materials in areas that are subject to unacceptably high corrosion attack. Indirect methods also can be employed to monitor corrosion in process-plant equipment. These parameters can be controlled within predetermined limits to minimize corrosion attack. Editors. pH. crevice corrosion. Traditional periodic monitoring techniques are typically part of plant maintenance and in-service inspection programs..V. Information from continuous monitoring can indicate when process parameters are outside of the target range. 1-306. If a suitable model of the corrosion process is available. Shah. Amsterdam. These periodic methods are economic to use but they do not provide rapid feedback on changes or upsets in the environment or manufacturing process that may significantly affect the integrity and reliability of operating equipment.. Corrosion monitoring also provides an effective means of process control. rather than by general corrosion. which allows plant operators to address potential problems in timely manner and avoid costly unscheduled shutdowns for repairs and replacements. Elsevier Science Publishers B. and hydrogen permeation. New York. P. Corrosion monitoring should be an essential element of plant-reliability programs. Technology for the ‘90s. such as pitting. References 1. commercially available. These emerging methods often employ more costly instrumentation and more complicated analytical procedures than the established methods. Part I • Plant Life Management and Aging. Corrosion monitoring can be used to monitor process conditions. but with continued research and development. For this reason. conductivity. many major corrosion problems are caused by localized attack. a formulation of the model can be incorporated into a computer system along with feedback signals from transducers that measure the indirect parameter. The effects of proposed changes in operating conditions on key plants components can be evaluated by using corrosion monitoring during trial runs. . The American Society of Mechanical Engineers. E. pp. However. and stress-corrosion cracking. and MacDonald. economic instrumentation and techniques for general corrosion monitoring are wellestablished. Thus. N. 1993. temperature.. July.Improving Plant Reliability Through Corrosion Monitoring 13 monitoring pitting and stress-corrosion cracking are valuable tools for monitoring localized corrosion. their industrial use should increase and eventually become widespread.
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