Engineering Failure Analysis 28 (2013) 6977

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Caustic corrosion in a boiler waterside tube: Root cause and mechanism

Farhad Daneshvar-Fatah, Amir Mostafaei , Reza Hosseinzadeh-Taghani, Farzad Nasirpouri
Laboratory of Failure Analysis, Research Centre for Advanced Materials and Minerals Processing, Department of Materials Engineering, Sahand University of Technology, Tabriz, Iran

a r t i c l e

i n f o

a b s t r a c t
We report a failure occurred in a boiler tube of low alloy steel, SA-210 Grade A-1. A severe thickness reduction was detected in a boiler tube during periodic investigations. Two identical parallel grooves along the horizontal tube were observed. The inner surface of the tube consisted of three distinct parts: (1) dark gray scale under the grooves, (2) hemi-elliptical grooves, and (3) brown porous scale above the grooves. Microscopic investigations and microhardness tests revealed that the microstructure and properties of the base metal is intact along the tube. Moreover, some needle shape crystals which represented Na2FeO2 and NaFeO2 compounds were observed in SEM images taken from the groove scale. An excessive amount of Na and Cu was detected by EDS in the groove. The XRD results conrmed the presence NaFeO2 which is the main product of caustic corrosion. Therefore, it was concluded that the evaporation at the waterline of the partially lled tube leaded to locally caustic concentration which dissolves the protective magnetite layer and subsequently attacked the bare metal. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 4 July 2012 Received in revised form 6 September 2012 Accepted 12 September 2012 Available online 13 October 2012 Keywords: Failure analysis Metallurgical examination Boiler tube Caustic corrosion Low alloy steel

1. Introduction Boiler failure is a major concern in power plants and other industrial units [13] and the tube corrosion is known to be the main cause. The total cost of boiler tube failures in power plants is estimated to be about $5 billion a year [4]. For ensuring long term and convenient operation of the boiler, water hardness and contaminant control is vital. The water treatment process begins with initial step of clarication and ltration in which suspended solids are separated from the water. Then the water passes through a resin bed (mostly zeolite) and hardness ions (Ca2+ and Mg2+). In the next step by heating the feedwater the solubility of the dissolved gas is reduced so the water is deaerated. Thermal deaeration can reduce feedwater oxygen concentration to less than 7 ppb. The remained oxygen is removed by adding oxygen scavengers. The most commonly used oxygen scavenger for boilers are sodium sulte and hydrazine. The most common internal water treatment programs applied to the boiler are: (1) phosphate treatment, (2) caustic treatment, and (3) amine or polyamine treatment. To decrease the susceptibility of corrosion, the pH of the boiler water should be maintained in the range of 911. Addition of alkaline agents such as sodium hydroxide (12 ppm) and sodium phosphate (Na3PO4) to the makeup water is a common treatment for providing the immune alkaline environment. Moreover, this alkaline environment contributes to formation of nonadherent sludge. It should be considered that above 93 C, NaOH can act as a severe corrodent to steel [5]. Scale deposits in boiler system are a main concern since they considerably increase the fuel consumption. In order to control the scale formation, phosphates are used to form controllable participates (phosphate treatment). Phosphate reacts with calcium and magnesium to form a soft particle which can be suspended in the boiler water and removed through blowdown. Chelant and dispersant programs are other common methods to control the scale formation [6].
Corresponding author. Tel.: +98 9126216801.
E-mail addresses: amir.mostafaei@gmail.com, a_mostafaei@sut.ac.ir (A. Mostafaei). 1350-6307/$ - see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.engfailanal.2012.09.010

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Moreover, phosphate addition to the makeup water prevents the formation of concentrated free caustic. However, as a result of improper maintenance, phosphate hideout and subsequently free caustic formation may occur. Due to evaporation, local concentration of caustics can reach to 10100 mg/l which leads to caustic corrosion or caustic embrittlement. In general, in the case of caustic treatment, use of excessive alkalines such as NaOH may lead to corrosion attack (caustic gouging and stress corrosion cracking) [5,7,8]. Caustic embrittlement which also referred to as caustic cracking is a form of stress corrosion cracking that takes place in highly concentrated alkaline environments. This brittle failure is common at welded joints in which there is excessive residual stress [912]. Caustic corrosion, also known as caustic attack or caustic gouging, is one of the most common causes of boiler tube failures [4]. In boiler tubes, generally due to evaporation, caustics compounds such as sodium or potassium hydroxides concentrate locally. Once the pH exceeds 12.9, highly concentrated caustic solution dissolves the protective magnetite lm and attacks the bare steel. Khajavi et al. [13] recommended that in order to eliminate formation of corrosion products, the molar ratio of free caustic sodium to phosphate should not exceed 2.6. Additionally, they also reported that if the ratio goes under 2.2, phosphate corrosion will occur which is apparently similar to caustic corrosion. In this current study, failure analysis of a boiler tube was investigated by visual inspection, X-ray diffraction (XRD), microhardness testing and microstructure studies using optical microscopy and scanning electron microscopy (SEM) equipped with energy dispersive X-ray (EDS). Based on the results and discussions, a possible mechanism for under deposit corrosion in this study was proposed. 2. Experimental procedure 2.1. On-site inspection The boiler was out of service for a few months and the tubes were washed by caustic compounds for scale removal. When the boiler was idle, wet lay-up method was applied to prevent the corrosion. In this approach, all the tubes were completely lled with demineralized and deaerated water. The water was also treated with sodium hydroxide to establish a pH of at least 11 and oxygen scavenger (sodium sulte). After repairs and several water ush-outs, the boiler was restarted and worked for 4 months. During operation, boiler water was under phosphate treatment. For providing the proper alkaline environment, sodium hydroxide was used. Sodium sulte was added to the storage space for deaerating heater. It was reported that at the beginning of the operation, water analysis showed unusual uctuations in pH and conductivity. Operators carried out several blowdowns to control the water chemistry. During periodic investigations, a severe thickness reduction was detected in a horizontal boiler tube by non-destructive testing (NDT). It was reported that there was a uniform oxide layer on the outer surface of the tube. Moreover, two parallel longitudinal trenches were observed on the internal surface. In order to examine the internal surface of the failed tube, a part of it was cut lengthwise and sent to the laboratory. 2.2. Characterization methods Three samples from different parts of the as-received specimen were selected for quantometric, metallographic, electron microscopy, X-ray diffractometery and hardness examinations. Furthermore, the oxide layer composition and corrosion products were analyzed. Spectroscopic methods were utilized as follows: (i) Chemical composition. To specify the chemical composition of the tube, quantometric analysis was applied. (ii) Optical microstructure studies. For microstructural examination, specimens were cut cross-sectional from the adjacent and apart from the groove. The samples were then mounted and polished. After preparation, the samples were etched by nital 2% solution for 15 s to study the microstructure morphology of the sample. (iii) Microhardness measurement. Vickers microhardness test was performed by Akashi (M400 G1 Leco) under indentation load of 100 g for 15 s. (iv) Electron microscopy analysis. The scanning electron micrographs of samples were analyzed using SEM (MV2300 Cam Scan), equipped with an energy dispersive X-ray (EDS-Oxford instrument). (v) XRD analysis. The X-ray diffraction (XRD) patterns were recorded on a D8 Advance-Bruckers AXS diffractometer with 0 Cu Ka radiation source (k = 1.54 A ) operated at 40 kV and 40 mA in the 2h range 10110 at the scan rate of 0.05 /s. 3. Results and discussions 3.1. Visual inspection An image of the as-received tube is shown in Fig. 1 which presents three perspective of the sample: (a) inner side, (b) outer side and (c) cross section images of the damaged tube. Based on the appearance and the color of the scale around the groove, the tube could be separated to three distinct parts (Fig. 1a). As it can be seen in Fig. 1a, on the inner side of

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Fig. 1. The as-received failed superheater tube: (a) inner side view, (b) outer side view and (c) cross sectional view.

the tube, there was an adherent gray scale (part A) and on the other side of the groove, there was porous brown scale (part B) which can be attributed to the formation of magnetite (Fe3O4) and hematite (Fe2O3), respectively. On the outer surface of the tube (Fig. 1b), an adhesive, uniform, and relatively thick oxide layer formed and there was not any sign of seam or weldment on the tube. From Fig. 1c, it is clear that the maximum thickness reduction is approximately 40% and the trench is rather elliptical. 3.2. Chemical composition analysis The quantometric analysis result is given in Table 1. With regard to the chemical composition, the tube was made of low alloy steel, SA-210 Grade A-1. 3.3. Metallographical examination The microstructure and morphology of the tube at the damaged region was examined by optical microscopy and the images are shown in Fig. 2. Metallographical images after polishing and etching procedure showed that the morphology of the tube at the center of the sample consisted of pearlite islands in ferritic matrix (Fig. 2a). Fig. 2b and c represents the area adjacent to the groove; no microcrack was observed, the scale layer is smooth and free from pits. Finally, Fig. 2d illustrated an optical micrograph taken from the groove region. By comparing Fig. 2ad, one can deduce that there were no changes in the microstructure and it is uniform along the tube, and the grain boundaries remained intact. 3.4. Microhardness test The microhardness tests were carried out on the cross-section of the sample in different distances from the groove. Microhardness prole of the specimen is represented in Fig. 3. As it can be observed, there is not any signicant difference in the hardness values. The brief results are given in Table 2. 3.5. SEM and EDS examination SEM was used to study morphology of the oxide layer and corrosion products. Fig. 4 shows the cross-section micrograph of the tube at the groove region. As it can be seen, the deposits on the surface of the base alloy consist of two different layers;
Table 1 Chemical analysis of the failed boiler tube. Component Wt% C 0.15 Si 0.19 P 0.015 Mn 0.52 S 0.004 Cr 0.03 Ni 0.02 Mo 0.02 Fe 99.051

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Fig. 2. Metallographic structures of the tube taken from (a) the center of the sample, (b) the area adjacent to the groove at dark gray scale, (c) the area adjacent to the groove at brown scale and (d) the groove region. All micrographs are in 500 magnication.

Fig. 3. (a) The corresponding image and line scan on which the hardness was measured and (b) the hardness prole of the tube.

F. Daneshvar-Fatah et al. / Engineering Failure Analysis 28 (2013) 6977 Table 2 Microhardness test results in different distances from the groove. Distance from the groove (mm) Hardness (HV) 12 160 10 159 8 160 6 158 4 159 2 158 0 159 2 159 4 160 6 159 8 159 10 158 12 159

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a relatively thick layer adjacent to the base metal which probably contains products of a severe corrosion attack (A), and a relatively thin uniform layer (B). Additionally, EDS results showed that in dark gray region, weight percentage of some elements such as Cu, Ca, Zn and Na is higher than brown area which can be attributed to presence of them in boiler circulating water. Surface of the tube at three regions (as determined in Fig. 1a) were studied using SEM. No microcrack was observed on the surface of the specimen in different areas. Figs. 57 show SEM micrographs taken from groove groove region, brown scales and dark gray scales, respectively. As it can be observed, there were some needle shape crystals on the groove scales (Fig. 5) which did not exist on the hematite layer Fe2O3, (Fig. 6) and magnetite layer, Fe3O4 (Fig. 7). EDS was utilized to identify the corrosion products on the inner side of the tube. The EDS samples were chosen from the groove, brown and dark gray scales. Three points was analyzed in each sample and the average is reported in Table 3. Elements such as Al, Zn, P, Cu and Ca were detected in an abnormal amount. A signicant amount of Na also was detected in the groove scale which conrmed presence of the caustic compounds in treatment water. Si, Mg, Ca are common water contaminants which remain in the feedwater or makeup water even after ltration. Cu is sometimes added to the makeup water intentionally due to its great conductive properties. Al presence can be attributed to copper base alloys and zeloite that is used for boiler water treatment. Moreover, oxygen scavengers which are used for water deaeration may contain sulfur. Finally, as mentioned before, the source of Na and P is chemicals that are used for boiler water treatment [13]. 3.6. XRD examination Qualitative analysis of deposits at the groove region was carried out by XRD. For sample preparation, the damaged surface was scraped and the prepared oxide powder was used. The XRD result is depicted in Fig. 8. It is clear that the groove scale mostly consist of magnetite and hematite. Moreover, presence of Cu, Cu2O and NaFeO2 was conrmed by XRD. 3.7. Root cause and mechanism of the boiler failure Generally, it was reported that there are three under deposit corrosion namely: (1) hydrogen damage, (2) acid phosphate corrosion and (3) caustic gouging. All of them need heavy deposits and a concentration mechanism within those deposits [8,13,14]. For hydrogen damage, the concentrating medium is usually chloride and contaminant levels are sufcient to corrode the protective oxide layer (magnetite and hematite). Moreover, hydrogen atoms can easily penetrate in carbon steel

Fig. 4. SEM image of the cross-section of the groove region, where a two layered deposit is formed on base metal: porous corrosion products (part A) and uniform scale (part B).

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Fig. 5. SEM micrographs of the groove region at two different magnications.

Fig. 6. SEM micrographs of the brown region (hematite layer) at two different magnications.

Fig. 7. SEM micrographs of the dark gray region (magnetite layer) at two different magnications.

F. Daneshvar-Fatah et al. / Engineering Failure Analysis 28 (2013) 6977 Table 3 EDS elemental analysis of the inner surface of the tube from the different part of the specimen. C Groove scale Brown scale Gray scale 2.75 1.84 2.04 O 21.21 18.98 24.90 Zn 1.09 0.11 0.39 Cu 8.06 1.27 3.93 Mn 2.16 0.64 1.49 Si 0.80 1.31 1.00 S 0.83 0.24 0.49 P 1.06 0.10 2.16 Ca 3.90 0.61 2.02 Al 4.16 4.62 4.50 Na 2.70 0.22 0.65 Ni 0.53 0.24 0.39 Fe 50.75 69.82 56.04

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Fig. 8. X-ray diffraction pattern of the corrosion products powder at groove region.

matrix. Then, hydrogen atoms tend to combine and form H2 molecules which cause distortion in structure and increases stress in the metal matrix. In decient phosphate treatment, the sodium to phosphate molar ratios (Na:PO4) may goes below 2.2 which leads to acid phosphate corrosion. Khajavi et al. [13] reported that when a solution of phosphate compound such as trisodium phosphate is concentrated at high temperature, precipitation of disodium phosphate crystals appears and the liquid would be rich in NaOH. Also, due to presence of phosphate anions in the water, monitoring and control of pH is complicated and the situation is prepared for acid phosphate corrosion. In the following equation, production of NaOH is presented:

Na3 PO4 H2 O $ Na2 HPO4 NaOH

When hydrogen damage and acid phosphate corrosion are common failure mechanisms in boilers, caustic treatment is the best solution to prevent them. However, if the monitoring and control of the boiler water pH are not undertaken properly, excessive amount of NaOH may enter the boiler water and caustic gouging will be inevitable [8,15]. On the other hand, insufcient NaOH dosing may leads to phosphate attack and formation of undesired scales. There are two main factors in occurrence of caustic corrosion: (1) presence of caustics in boiler water and (2) concentration mechanism. With respect to the water treatment program applied, caustic soda was added to the water. Moreover, after restarting the boiler, several load changes was recorded. Load change is one of the main causes of phosphate hideout in which phosphate precipitates and consequently free caustic may form [13,16]. Therefore, as a result of load changes and bulk phosphate hideout, boiler water analysis had shown unusual uctuations. By blowdowns the operators tried to control the water chemistry, but the operating pressure was not changed. This situation leaded to water/steam stratication and formation of waterline in horizontal tubes. Above the waterline a high heat ux area formed and the water in contact with the tube wall at the surface evaporated rapidly leaving behind contaminants. Under these conditions, dissolved solids such as NaOH or suspended solids such as copper, began to concentrate. Simultaneously, phosphates accumulate in the concentrated liquid and precipitated or reacted with surface scales. Then the locally concentrated NaOH at the waterline attacked the protective oxide layer and bare metal. The EDS results show a signicant amount of Na in the trench scale. The iron oxide which is formed on the inner surface of the tube is an amphoter compound and it is susceptible to be attacked by sodium hydroxide. At temperatures above 90 C, the concentrated NaOH attacks into the protective magnetite lm by the following reaction:

Fe3 O4 4NaOH ! 2NaFeO2 Na2 FeO2 2H2 O

In some literatures, the following reaction for dissolving the magnetite layer in caustic solution is also recommended [17,18]:

3NaOH Fe3 O4 ! 3NaFeO2 H H2 O

Gradually, the highly concentrated NaOH dissolves the protective magnetite layer based on reactions 2 and 3, and the bare iron reacts with NaOH according to the following reactions:

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Fig. 9. Scheme of caustic gouging along a longitudinal waterline where the tube was not lled completely.

NaOH H2 O Fe ! NaFeO2 3H 2NaOH Fe ! Na2 FeO2 H2

4 5

As a result of Eqs. (3)(5), Corrosion of base metal is taken place by gouging. According to these equations, although generation of hydrogen can cause hydrogen damage, it has not been conrmed in practice [18]. In caustic solution, hydrogen produced by dissolving the bare metal move to the solution instead of penetrating to the base metal which is common in acidic electrolytes. Meanwhile, the base iron tries to restore the magnetite lm and consequently a porous non-protective magnetite layer is formed. After elimination of the protective lm, the caustic solution enters the oxide layer. The trapped solution evaporates and consequently, pH beneath the oxide layer increases. Fig. 4 clearly represents the diffusion of caustic solution inside the magnetite layer which causes formation of a two layered scale on the base metal. Furthermore, it is reported that in caustic solutions, Na2FeO2 and NaFeO2 crystals are needle shape which can be observed on the remained trench scale (Fig. 5). From the appearance of the oxide layers in Fig. 1a, one can deduce that the brown and dark gray oxide layers mostly consist of hematite and magnetite, respectively. It should be considered that magnetite often forms in aqueous environments. With respect to the position of dark scale and higher amount of elements within it, one can conclude that the tube has been partially lled with water through the boiler operation. By studying the morphology of the deposits (Figs. 57), it is clear that uniform layer was formed on the inner side of the tube. Although grain boundaries are highly susceptible to corrosion attacks such as stress corrosion cracking or intergranular corrosion, there was no evidence of microcrack. Metallographical studies (Fig. 2) showed that the grain boundaries adjacent to the trench are intact and no microcracking or hydrogen damage evident has appeared. The microhardness test results which are presented in Table 2 showed that the properties of the region adjacent to the trench are similar to the parts relatively far from it. Thus, results indicated that pitting corrosion, hydrogen damage, stress related corrosions, and oxygen attack did not occur. Fig. 9 presented the scheme of caustic gouging along a longitudinal waterline where the tube was not lled completely. In steam generating systems such as boilers, copper is extensively added to the makeup water for water heating, steam condensing and process temperature control [13]. When copper is dissolved or present as oxide particulate form in boiler water, usually deposits in metallic form. For instance, cuprite (Cu2O) and the cupric oxide (CuO) reduce by the following reactions and intensify the corrosion [18]:

CuO 3Fe ! 4Cu Fe3 O4 4CuO 3Fe ! 8Cu Fe3 O4

6 7

Therefore, copper is deposited either by direct exchange with iron or by reduction of copper oxide by hydrogen evolved during corrosion. It is common to see large reddish stains of elemental copper intermixed with corrosion products such as magnetite and hematite near caustic corrosion sites because of the hydrogen generation associated with the attack [16]. In a partially lled tube, rapid evaporation of the water at the surface, accelerate deposition of mineral precipitates and particulates such as calcium and copper. Other parameters such as pH, temperature, ow rate, amine type, amine concentration, and dissolved oxygen concentration impact copper concentration in deposits [13]. 4. Conclusion and recommendations In this study, the tube was lled in half of its content. Moreover, High heat ux causes increased deposition in which any liquid water contacting the hot-side tube wall is vaporized. Therefore, concentration of the caustic compound and other minerals, which are present in water, increases in deposits. Again, water diffuses into these scales and evaporates due to high heat ux, and consequently, the amount of caustic compound, which are extremely corrosive, increases in the waterline area and nally leads to gouge. Finally, two identical parallel trenches were observed in horizontal tube of a boiler unit. Visual inspections, metallurgical and morphology examinations, and composition analysis of scales showed that the failure is due to evaporation of water inside the partially lled tube and concentrating of caustics at the water surface that leads to caustic gouging along the waterline. However, metallographical and SEM results did not reveal any crack in microstructure of the tube in different regions.

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In order to prevent or postpone this problem, following suggestions are presented: 1. Precise control of water treatment and coordinated phosphate programs and caustic treatments which can prevent formation of the free caustic. Also, unintentional release of caustic regeneration chemicals from makeup water demineralizers should be prevented. 2. By controlling the boiler load, it can be possible to prevent formation of waterline at horizontal tubes. 3. General inspection of the tube for nding any thickness reduction in wall is necessary. 4. Prevent the creation of waterlines in tubes which may be created by excessive blowdown rates, low water levels, and excessive load reduction when pressure remains constant.

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