Development of on-line monitoring system for the Flow Accelerated Corrosion

Na Young Lee1, Seung Gi Lee1, Kyung Ha Ryu1, Il Soon Hwang1, Jung Taek Kim2 1 Seoul National Univ., 56-1, Shinlim, Gwanak, 151-742, Seoul, Korea Tel: 82-2-880-7200, Fax: 82-2-3285-9600, grasia2,sroba2, future1,hisline@snu.ac.kr 2 Korea Atomic Energy Research Institute, Daejon, Korea, jtkim@kaeri.re.kr Tel: 82-42-868-2404, jtkim@kaeri.re.kr ABSTRACT Aged nuclear piping has been reported to undergo corrosion-induced accelerated failures, often without giving signatures to current inspection campaigns. Several factors were known to affect the Flow Accelerated Corrosion (FAC) in the piping. They include material composition of the target material, temperature, pH, dissolved oxygen content, pipe geometry, flow velocity and geometry of the flow path. Therefore, we need to investigate various parameters to effectively monitor FAC. Also we need to cover wide area, since we dont know where the FAC will occur. In this work, we developed the electrochemical condition monitoring system. It can be used to predict the status of the piping by introducing wearing rate model. Using the model based on the monitored electrochemical parameters, we can predict quantitative thickness change. We need to measure the thickness in-situ to compare with. For this purpose, we adopted high-temperature Ultrasonic Transducer (UT). To validate the feasibility of the sensors for the Nuclear Power Plant (NPP) environment, we constructed test loop, which simulates the secondary part of the NPP. Through three-week validation test, we identified sensor applicability and performance to monitor the FAC environmental status. Thickness calculated from the wearing rate model, shows good consistency to the UT monitoring result. After the test, we cut the elbow part to measure the real thickness to confirm the results. As a future work, we are working on the development of direct thickness measurement system using Direct Current Potential Drop (DCPD) method, which we expect to cover broader area than UT in the high temperature condition. I. INTRODUCTION In the most Nuclear Power Plants (NPPs), mal-functions of active components have been main causes of trips. Therefore, most of maintenance concern was focused in the active components. As NPPs become aging, however, gradual degradation of passive components becomes a big problem. Since the piping rupture accident was reported at Surry Unit 2, there have been many incidents due to Flow Accelerated Corrosion (FAC). And it becomes worse because of aging. Non-destructive evaluation technique was introduced as a direct evaluation technique. It can be done during the overhaul periodically. But there are too many piping need inspection to cover during the short inspection time. Therefore the necessities of on-line monitoring for the passive components become increasing. Several factors were known to affect the occurrence of FAC in the piping. They include material composition of the target material, temperature, pH, dissolved oxygen content, pipe geometry, flow velocity, and so on. The flow path through elbows and other complex geometry which creates turbulence to weaken the protective oxide layer of carbon steel piping also contributes to accelerate the FAC process. In this work, we focused on electrochemical parameters, ECP and pH, and the thickness change of the piping. Since the elbow part is known to be susceptible to the FAC, we chose elbow part as a target system. We developed sensors suitable for each purpose and then tested. Electrochemical parameters are useful to inform whether the environment is corrosive or not. It gives qualitative information on FAC. Therefore, we adopted wearing rate model for the FAC as a function of monitoring parameters such as temperature, pH, flow velocity, geometrical factors. Using this, we can predict the thickness reduction in a certain electrochemical condition. Using this, we can predict the thickness change to compare with direct thickness measurement results. We chose Ultrasonic Transducer (UT) as a direct measurement method. We surveyed UT system for the on-line, high temperature application to directly monitor the thickness. It is required to validate the other test results. It can also be used for the FAC monitoring; however, it has a good resolution only for the narrow area, where it is installed. But, it is enough to support validation of the experimental results. To identify on-line applicability, we constructed FAC test loop and then performed validation tests for developed sensors.

These works are described in detail in the following sections. Preliminary works, including sensor surveillance and development of the wearing rate are described in the section 2, FAC experimental process is explained in the section 3, and the test results are discussed in the section 4. II. PRELIMINARY WORKS A. Wearing rate model for the electrochemical parameters FAC is a multi-variable phenomenon, so that it is insufficient to evaluate the FAC based on one variable. Piping material, geometrical configuration, flow rate, water temperature, water chemistry (pH, dissolved oxygen) are important parameters to evaluate FAC susceptibility. In this work, we concentrate on detecting electrochemical parameters of the target system. Electrodes for high temperatures are developed and pre-tested. [1,2] To predict the thickness of the piping by FAC, we introduced a wearing rate model and then modified it considering the test condition. Sanchez-Calderas Model is a theoretical model that can predict the rate of materials reduction induced by FAC, which is shown in the equation (1). [3, 4]

( Ce C ) dm = kg dt 1 1 + (1 f ) + k hD D
Where,
dm dt

(1)

represents wearing rate [kg/m2s]

kg is geometrical factor, 7.5 for elbow piping Ce is equilibrium concentration of iron species C is iron species concentration in the bulk water is porosity and 0.03 below 150 C k=Aexp[-Q/RT], the reaction rate constant f is fraction of oxidized metal converted into magnetite at the metal-oxide interface. f=0.5 hD is a mass transfer coefficient is oxide thickness, 10 m D is a diffusion coefficient of the dissolved ferrous species In the equation (1), kg is not included in the original Sanchez-Calderas model. It assumed straight pipe condition. To apply this model to complex geometry, such as piping elbow, kg was introduced. In the Kastner et.al.s work, which is an empirical FAC model, they introduced a geometrical factor. In that model, geometrical factor for piping elbow is around 7.5, while the value for straight piping is unity. [5] Ce is equilibrium concentration of iron species. To calculate the solubility of magnetite, Sanchez-Caldera introduced the work of Sweeton and Baes [6] that provides the experimental data on the solubility of magnetite as a function of temperature, hydrogen concentration, and pH. In this work, we acquired the thermodynamic data for ferrous ions from the commercially available computer code, HSC Chemistry . Here, we assumed the iron species concentration in the Bulk Water, C as negligible. All other values were adopted from references. [3, 4, 8, 9] By this way, all the variables used in the equation can be expressed as a function of temperature, fluid velocity, dissolved hydrogen and pH. The normal water chemistry of secondary coolant system is deaerated with hydrazine and slightly alkaline with ammonia. In a laboratory-scaled experiment, acceleration test should be conducted due to the limit of available time. Therefore, we consider a slightly reducing environment with 150 ppb hydrogen and acidic solution. The pH of test solution is one of key parameters in the acceleration test. There are certain regions where corrosion is accelerated or activated. Figure 1 shows the predicted wall thickness reduced by FAC as a function pH, which is based on modified Sanchez-Calderas model. In the calculation, test duration is assumed as two weeks. Based on the wearing rate model, we can predict the reasonable test duration. We can also extract other test conditions, such as temperature, flow velocity as well as pH, once we fixed the test duration.

7 6

Thickness reduction, mm

5 4 3 2 1 0 -1

Modified Sanchez-Caldera's model T=125C, Flow velocity 3 m/s Operation for 2 weeks

3.5

4.0

4.5

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6.5

pH

Figure 1 Predicted thickness reductions with pH B. Feasibility Check for Ultrasonic Transducer UT is introduced to measure the thickness directly during the validation test of electrodes. Since the monitored ECP and pH can be converted to thickness change by wearing rate model, we need to monitor the in-situ thickness of the piping. Chosen transducer has a shoe structure in front of the transducer to mitigate the temperature effect. But the signal reflected on the shoe surface is too big compared with that of the target material. Signal attenuation is also problematic. The most troublesome is that the target surface is round and the contact area is too small. And it is difficult to monitor exactly the same location once we move UT sensor. Therefore, we installed UT support structure to fix the monitoring point.

(a)

(b)

Figure 2 (a) Flattened surface of the test specimen (b) UT installed at the elbow surface Since we installed UT at the round surface of the piping, the reflected signal is very weak. It becomes worse since we also used a shoe structure by which the signal attenuation is increasing. When we measure the thickness of the larger piping with 80cm diameter and 30 mm thickness, it works fine. To improve the signal reliability, we decided to flatten the outer surface of the test target by machining. Figure 2 shows the flattened surface and the sensor installation with fixing structure.

III. EXPERIMENTAL In this work, we designed the test loop to accelerate the FAC to induce continuous thickness change. By doing this, we expected to identify on-line applicability of sensors. FAC rate is the highest when the environmental temperature is between 130-150C. Validation test was conducted slightly lower temperature around 125 C. Testing flow velocity was 3 m/s and pressure was 20 bars to simulate the secondary part of the NPP. However, not like a NPP condition, we chose low pH to accelerate the FAC rate. FAC is also affected by geometrical factor. We chose piping elbow as a testing target, which is the most flow-affected region. Testing material was carbon steel. It is reported that if the contained Chromium weight is more than 0.04 %, FAC rate becomes steeply decreased. Since we cannot find carbon steel elbow piping with Cr content under 0.04%, we bended carbon steel piping contains 0.01% Cr to elbow shape.

Figure 3 FAC test loop We constructed FAC test loop to perform the on-line feasibility test for developed sensors. It is shown in the figure 3. It is composed of two separate skids: one has both charging and circulation pumps and it is connected by flexible tubes to isolate the vibration effect of pumps. On the first skid, we installed water tank to supply chemically controlled water. Two sets of Electrodes were installed to monitor the chemical conditions around the elbow piping. Each set is composed of ECP and pH electrode.

Figure 4 Monitoring screen for the FAC test loop In the figure 4, we showed the monitoring screen for the FAC test loop. It shows overall structure of the test loop and important monitoring parameters of each location. It can be classified as following: First, it shows environmental monitored parameters such as temperature and pressure at each section of the test loop. Second, it shows the on-off status of active components, such as heaters and pumps. Third, it shows the monitored values of two sets of electrodes. Monitored voltage

values are converted to pH and ECP values and displayed in the screen. It also shows whether the operating condition is active or passive to corrosion. Using the wearing rate model, we estimated test duration. In the wearing rate model, we fixed all the other parameters except for pH. We decided to use HNO3 and HBO3 to achieve the required low pH. We used MULTEQ code to calculate the required amount of chemicals. [9] In the preliminary test, however, monitored pH value was higher than we calculated. At the beginning, monitored pH was the same with the calculated value. After some time, it becomes higher over the test condition. We investigated test conditions and electrodes thoroughly to find the reason. When we recalculated the pH considering iron oxidation reaction, which releases OH-, we found pH was drastically increased. It is shown in the figure 5. It increased steeply when we assumed the reaction, and then saturated. So, we determined the initial test pH lower than planned to achieve the expected pH.
8 7 6

pH
4

Fe + 2H 2 O Fe 2+ + 2OH - + H 2
0 200

Fe

2+ 400

concentration, ppm

600

800

1000

Figure 5 pH changes with iron IV. TEST RESULTS AND DISCUSSION

oxidation

FAC tests were performed three times. From the first and second test experience, we improved test loop and procedure. Third FAC test was originally planned to continue for two weeks. However, the reduction rate is lower than we expected, and thus, we performed test for three weeks including pre-conditioning. Test objectives are as following: 1. Identify sensor applicability to high temperature and performance to monitor the FAC environmental parameters and also the thickness. We also checked the possibility of on-the-pipe installation 2. Validation of the FAC environmental condition design. Check the validity of the setting values for the overall test condition including electrochemical parameters to induce more than 10% of thickness change, which corresponds to the resolution target of sensors. 3. Validate FAC wearing rate model with monitored parameters. Using wearing rate model, thickness can be calculated with monitoring parameters. We can compare the calculated value with UT measurement to validate the monitoring results. A. Evaluation of electrodes

We installed two sets of electrodes to monitor ECP and pH. Figure 6 shows the monitored electrochemical parameters. It was maintained in the corrosive region of the ECP-pH diagram as shown in the figure 7. When the test started, measured pH increased far over than we expected, as shown in the figure 6. This was investigated from the 1st and 2nd day of the FAC tests. We assumed that the increase of pH is caused by the iron oxidation reaction described in the previous section. Therefore, we lowered the pH after the startup which induced the pH to decrease afterwards.

(a) Monitored ECP

(b) Monitored pH Figure 6 Monitoring results: ECP and pH

Figure 7 ECP-pH diagram with monitoring region

7.0u

8.0u

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Thickness measured by UT(mm) Amplitude [V]

1.1
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1st day 6th day 12th day

1.0
0 0

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period 1st day = 0.41us 6th day = 0.354us 12th day= 0.29 us
7.0u 8.0u 9.0u

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200 Time [sec]

300

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500

Elapsed time(hr)

(a) UT signal during the test Thickness measurement using UT Figure 8 Thickness measurement using UT

(b)

From the derived wearing rate model, we found that the reduction rate increased, when operating pH level is below 4. We check the thickness everyday using UT monitoring system. Figure 8 (a) shows monitored UT signals during the test. We compared thickness data of the 1st, 6th and 12th day. Figure 8 (b) shows the converted results from UT. It shows the thickness reduction as a function of time. There are two steep decrease regions in the curve, which will be discussed in the next section. B. Thinning and UT monitoring results We investigated the possible reasons of discrete reduction rate.

First, UT resolution was reconsidered. In the original plan, the thickness of the test specimen was 3.6 mm. To improve the UT performance, however, we grinded the piping surface to 1.3 mm. 5Mz transducer was used in this work. Considering the thickness of the specimen, we had better use UT with higher frequency. But, to prevent the signal attenuation, we used transducer of 5 MHz, sacrificing the resolution. It can be one reason of steep change of the thickness. Second, flow induced erosion was proved to be severe to break the corroded surface into pieces. Figure 9 shows the cutting face of the corroded elbow specimen. Elbow piping was removed from the test loop after the test duration and then cut. When we investigated the surface, it shows the clear evidence of FAC occurrence. Inner surface was corroded and showed partly removed surface as if it is eroded. It can be one reason of the discrete change of the thickness. Third, change of chemical environment is suspected since the steep decreases were occurred when we changed the water supply tank. When we changed the water tank, small amount of oxygen might be also inserted. Dissolved oxygen level was monitored using DO (dissolved oxygen) meter. But monitored ECP doesnt change much, which shows that the effect of DO is negligible.

Figure 9 Inner surface of the elbow specimen Reduced thickness was measured from the center cut using micrometer to compare with UT monitoring result. Thickness measurement results both by micrometer and UT are summarized in the Table 1. Table 1 Summary: Monitored thickness Initial thickness of the elbow (error 5.5 %) Micrometer UT monitoring Micrometer UT monitoring 1.27 mm 1.2 mm 0.94 mm 0.8 mm

After 3 weeks of FAC experimental (error 14.9 %)

Monitoring locations of UT and micrometer are not exactly the same. We welded support structure for the UT sensor on the surface of the elbow specimen to fix the monitoring location. However, it is hard to measure the exactly the same location using movable micrometer. Although we measured several times and then used the mean value, it should have differences between each measurement. But the measured and monitored values are close and we assumed that it is reasonably acceptable. C. Comparison between Model and Monitoring Results When we calculated the thickness reduction rate using Sanchez-Calderas model, we assumed constant pH. But, it changed during the validation test. All the electrochemical monitoring parameters are stored in every 10 seconds during the test duration. Since pH is the major parameter that affects the wearing rate, we calculated the mean value of pH in a daily basis. We calculated the amount of thinning everyday, and then accumulated for the test duration. It is plotted in the figure 10.

1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 -0.1

100

200

300

400

500 6

Thickness, mm

pH pH

UT measurement S-C model calculation

0 100 200 300 400 500

Time duration (hour)

Figure 10 Comparison between monitored thickness and prediction model In the figure 10, we showed the mean pH, thickness predicted from the model, and the UT monitoring results. It showed clear reduction of the thickness when the pH was lowered. After 250 hours of operation, however, measured and predicted values showed different trend. The model indicated continued reduction, whereas UT monitored result indicated no more reduction afterwards. According to the model, piping should be penetrated, which is not. We reviewed the model again. In the equation (1), we assumed C as negligible. If the FAC rate increased, however, ions in the bulk water would increase. It means that C becomes no more negligible. As time passed, ion concentration in the bulk water would build up until close to Ce, which would mitigate the reduction rate V. CONCLUSIONS In this work, we developed FAC monitoring system for the piping elbow in the secondary part of the NPP. Requirements for the developed systems are as following. High temperature, geometrical applicability On-line applicability (long time performance) Resolution required to identify the change

Considering the environment, diverse sensors other than introduced in this paper, were suggested. To validate chosen sensors, we designed test loop and then tested. To convert the monitored electrochemical signals to quantitative thinning, we introduced wearing rate model. UT system was installed to generate the comparison data. Monitored values from Electrodes were used as inputs to the model and converted to thickness reduction to predict the remained thickness. Then, it was directly compared with UT monitoring results. Sensors showed good on-line performance for three weeks of test duration. Monitored signals, converted to thickness using model are consistent to the reference UT data. As a future work, we are developing the Switching Direct Current Potential Drop (DCPD) method to measure the thickness of the piping. It can cover broader area than UT and applicable to the high temperature environment. Based on the Finite Element Analysis (FEA), it is expected to effectively monitor the piping degradation. It was preliminarily tested in the elbow piping, which showed consistent results with FEA. As a next step, we are planning to perform the same test procedure explained in this paper again with both UT and Switching DCPD system to identify the performance. ACKNOWLEDGMENTS This work was supported by Korean MOST and US DOE as one of I-NERI project. REFERENCES 1. C. B. Bahn, S. H. Oh, N.Y. Lee, I. S. Hwang, and J. T. Kim, Development of FAC monitoring system through electrochemical sensors, Proc. Korean Nuclear Society Autumn Meeting, Youngpyong, Korea (2002)

2.

Na Young Lee, Seung Gi Lee, Il Soon Hwang, Jung Taek Kim, Vincent K. Luk, Development of Integrated Monitoring System for FAC Monitoring, American Nuclear Society winter meeting, Pittsburgh, US, June. 2004 3. R. G. Keck and P. Griffith, Prediction of Erosive-Corrosive Wear in Low-Carbon Steel Piping Conveying Water or Wet Steam, ASME Journal of Engineering for Gas Turbines and Power, Vol. 112 (1990), pp.555-560. 4. L. E. Sanchez-Caldera, The Mechanism of Corrosion-Erosion in Steam Extraction Lines of Power Stations, ASME Journal of Engineering for Gas Turbines and Power, Vol. 110, (1988), pp.180-184. 5. Von W. Kastner and K. Riedle, Empirisches Modell zur Berechnung von Materialabtr gen durch Erosionskorrosion, VGB KRAFTWERKSTECHNIK 66, Heft 12, (1986), pp.1171-1178. 6. Antti Roine, Outokumpu HSC Chemistry for Windows: Chemical Reaction and Equilibrium Software with Extensive Thermochemical Database, Users Guide, Version 4.0, 1999. 7. F. Sweeton and C. Baes, The Solubility of Magnetite and Hydrolysis of Ferrous Ion in Aqueous Solutions at Elevated Temperatures, J. Chem. Thermodynamics, Vol. 2, (1970), pp. 479-500. 8. R. Mills and V. M. M. Lobo, Self-diffusion in electrolyte solutions: a critical examination of data compiled from the literature, ELSEVIER, 1989, pp. 320. 9. C. Cragnolino, A Review of Erosion-Corrosion of Steels in High Temperature Water, Proc. 3rd Environmental Degradation of Materials in Nuclear Power Systems-Water Reactors, Ed. G. J. Theus and J. R. Weeks, The Metallurgical Society, Traverse City, Michigan, 1987, pp. 397-406. 10. MULTEQ: Equilibrium of an Electrolytic Solution With Vapor-Liquid Partitioning Volume 3: Theory Manual, EPRI NP-5561-CCML Volume 3 (Palo Alto, CA: Electric Power Research Institute), 1992.