Experimental Study and Numerical Modeling of Erosion-corrosion of J55 Steel in Brine of Huanghe (Yellow) River Valley Dajun Zhao1,2, Zihang Sun1,2, Yan Zhao1,2,*, Xiaoshu Lü1,2,3 and Xianfeng Tan4 1College of Construction Engineering, Jilin University, Changchun 130026, P.R. China Laboratory of Drilling Technology in Complex Conditions of Ministry of Land and Resources of the People’s Republic of China, No. 938 Ximinzhu Street, Changchun 130026, P.R. China 3Department of Civil and Structural Engineering, School of Engineering, Aalto University, P.O. Box 12100, FIN-02150, Espoo, Finland 4Shandong Provincial Lubei Geo-engineering Exploration Institutes, Dezhou 253000, P.R. China 2Key ABSTRACT: Fluid field can have significant effects on corrosion rates of steels. The objective of this paper is to investigate erosion-corrosion mechanisms of J55 steel and the effects of local hydrodynamic factors, in particular, the fluid flow velocity on J55 steel’s service life. A new experimental setup was developed to specifically simulate the actual hydrodynamic conditions of Huanghe (Yellow) River valley. Computational fluid dynamics (CFD) model was adopted to characterize the hydrodynamic factors, such as the flow rate, the turbulence kinetic energy and the shear stress, and their effects on the corrosion behavior of J55 steel. Corrosion morphology was analyzed. Results show that the erosion rate increased with the flow rate and the resulting corrosion pit became smaller and deeper. Through the research results of this paper, it could provide some technical supports for the scientific and rational exploitation of brine. 1. INTRODUCTION J has been widely used as filter material in brine mining. In the presence of a large amount of Cl– , K+, Ca2+, Na+, Mg2+ in brine, J55 steel is extremely sensitive to corrosion damage. Erosion-corrosion of steel in brine mining is the most common cause of filter element failure [1–3]. The erosion-corrosion is known to be affected by a number of factors including the microstructure of the materials, the flow field, and the external stress distribution. In fact, changes in fluid flow rate induce changes in surface ions and stress in the mass transfer process, leading to a complex corrosion process. Studies show that the corrosion rates increase with flow rates [4–8]. High flow rate not only accelerates the general corrosion rate, but also causes local corrosion [9–11]. However, when the flow rate increases, the scour effect intensifies and washes the loose corrosion products, alleviating the alloy corrosion to some extent. The effects of flow rate and regime on erosioncorrosion morphology can further affect the flow field 55 steel/low carbon steel *Author to whom correspondence should be addressed. E-mail: [email protected]; Tel/fax: +86 431 8850 2678 in the erosion process, especially in the part of sudden change of flow field (corrosion pitting).When there is no corrosion product on the top of the material surface, the high flow rate increases the transmission rate between the materials and the medium, intensifies the erosion effect on the metal surface, and, hence, accelerates the corrosion rate. By contrast, if there is corrosion product film on the material surface, it can act as a barrier that reduces the mechanical damages of fluid on the material surface [6,7,9,12]. Therefore, corrosion rate is strongly related to material transport rate. If the product film is dissolved by chemical process and mechanical incision effect, the corrosion rate of the material rapidly increases. It is generally accepted that high flow rate causes the corrosion product film to become thinner [13,14]. High flow rate may form a thin but protective film by affecting Fe2+ dissolution kinetics and nucleation process of FeCO3 [13]. Schmitt’s study stated that the damage of fluid on corrosion product film could cause local corrosion [15]. The above studies demonstrate the profound influence of the hydrodynamic environments on the erosion corrosion process of the J55 steel. The local hydrodynamic factors, such as flow rate, regime and concentrations of Cl– , K+, Ca2+, Na+, Mg2+ in brine, interact Journal of Residuals Science & Technology, Vol. 14, No. 1—January 2017 1544-8053/17/01 235-09 © 2017 DEStech Publications, Inc. doi:10.12783/issn.1544-8053/14/1/28 235 236 D. Zhao, Z. Sun, Y. Zhao, X. Lü and X. Tan with each other to simultaneously influence the corrosion process [16]. Brines vary from mine to mine, and for this reason the local hydrodynamic factors in the Huanghe (Yellow) River valley is investigated in this study. As there is limited research on the effect of hydrodynamic conditions on erosion-corrosion of the J55 steel in general, the current work covers this gap via computational fluid dynamics (CFD) simulations and experimental validation. The experiments were set up to specifically simulate the actual hydrodynamic conditions of Huanghe (Yellow) River valley. As fluid velocity is one of the most important parameters affecting the corrosion rates, this study focused on the effect of fluid rates on the corrosion of J55 steel. CFD model was adopted to characterize the flow pattern within the reaction kettle in order to determine the correlation between the flow and the corrosion rates. The effects of corrosion morphology on the flow field and the distribution conditions of the flow with pits were studied using CFD simulations. 2. EXPERIMENTAL MATERIALS AND PROCEDURES Figure 1. The configuration of the corrosion test sample. rosion products. Then the weight loss rate of the test sample (ΔW, g cm–2 s–1) was evaluated using Faraday’s equation of general chemistry [17]: ∆W = (1) Where W: sample lost weight (g), A: exposure area (cm2), t: corrosion time (s) The weight change rate related to metal loss, ΔW (mg cm–2 d–1), can be then converted to an average penetration rate (P, mmy–1) using the relation below [18–21]: P= 2.1. Experimental Materials J55 steel of Φ300 mm (outside diameter) and wall thickness of 10mm was chosen as experimental material. Its nominal chemical compositions are shown in Table 1. The J55 steel was processed into the cuboid sample with size 140 mm × 30 mm × 5 mm, and then drilled at equal spacing. The diameter of the hole was 18 mm and the center distance was 40 mm. The circular hole was in the size of the field. The processed sample is shown in Figure 1. The sample surfaces were polished up to 1500 grit gradually with grinding paper in a clean and dry condition. Before and after the test, the sample was weighted (±1 mg accuracy). The employed solution was comprised of 110.1 Cl–, 1.52 K+, 1.02 Ca2+, 60.3 Na+ and 7.85 Mg2+ to simulate brines under local hydrodynamic conditions of Huanghe valley groups (Table 2) The corrosion test duration was 48 hours. The ultrasonic cleaning machine was used to remove the cor- W At 3.65∆W ρ (2) Which could be derived by dividing Equation (1) with the density of the metal. XL-30 (ESEM) FEG scanning electron microscope and Genesis 2000 energy dispersive spectrometer (EDS) were adopted to characterize and study the corrosion behavior of the sample. 2.2. Erosion-corrosion Test An erosion-corrosion device was designed to simulate the loop circulating conditions of J55 steel (Figure 2). It consisted of pipes, a centrifugal pump, a reservoir, a pressure gauge, a flow meter, a ball valve, a sample holder, and a reaction kettle. The solution was supplied from a 35 L reservoir and circulated through the centrifugal pump. Its flow velocity was controlled by the pump rotational speed using a speed controller. The material of the connecting pipeline (inner diameter 28 mm) was PPR pipe fitting. The material of both re- Table 1. Nominal Chemical Composition of J55 Steel (mass %). Table 2. The Chemical Composition of Brine (g/L). Element C Si Mn P S Ni Cu Content 0.18 0.20 1.25 0.015 0.007 0.162 0.20 Ion Content Cl– K+ Ca2+ Na+ Mg2+ 110.1 1.52 1.02 60.3 7.85 Experimental Study and Numerical Modelingof Erosion-corrosion of J55 Steel 237 Figure 2. Erosion Corrosion Device. action kettle and sample holder was organic glass and the inner diameter of the reaction kettle was 190 mm. The volume of the water pump was adjustable with the experimental pipe inlet flow rates of 0.677 m/s, 0.812 m/s and 0.947 m/s. A temperature control system was installed in the reservoir to control the temperature of solution. The testing temperature was set to be 70°C which was taken as the actual working temperature of the steel controlled by Pt100 resistance temperature detector. 2.3. CFD Simulation CFD simulation was used to investigate the flow field condition in the reaction kettle and the effect of the morphology (corrosion pitting) of the corrosion product film on the flow field. The simulation analysis was divided into two parts, overall simulation and local simulation. The overall simulation focused on the distribution of flow field in reaction kettle under the aforesaid condition. The model size to full size ratio was 1:1. The local simulation was performed for corrosion pitting. Figure 1 shows its location in the front face of the sample. The corrosion pit, of a cylindrical pit was measured 0.1 mm in diameter and 0.1 mm in deep. The fluid was assumed to be incompressible and a standard two-equation κ – ε turbulent model considering the Reynolds number of the flow, 27644 calculated according to the geometrical dimension of pipeline and flow velocity. The Reynolds number was much higher than 4000, indicating a turbulent flow. The turbulent kinetic energy κ was 1 m2/s2 and the turbulent dissipation rate ε was 1 m2/s3. The κ – ε turbulence intensity was set as 3.5%, obtained from Reynolds number. The turbulence equation was solved by iterative method with a convergence criterion of 0.000001. The mesh and boundary were set up according to the following conditions: Single phase flow model was used to determine distribution of flow field within the reaction kettle. The flow rate of the inlet was respectively corresponding to 0.677 m/s, 0.812 m/s and 0.947 m/s. The outlet was set as outflow. 3. RESULTS 3.1. Corrosion Performances 3.1.1. Corrosion Rate and Weight Loss Figure 3 shows the macro corrosion morphology at 238 D. Zhao, Z. Sun, Y. Zhao, X. Lü and X. Tan the flow rates of 0.677 m/s, 0.812 m/s and 0.947 m/s with obvious erosion marks (trace of dark scratch). The corresponding weight loss and penetration rate derived using Equation (2) are shown in Table 3. In all three samples, the position having the most serious corrosion was above the hole in the middle (see red circles of figure), where the opening for filtering water was the closest to the pipe inlet and the erosion intensity of the fluid was the maximum. Both Figure 3 and Table 3 demonstrate that the increasing flow rate led to a gradually growing weight loss and a penetration rate and a general higher corrosion. At the inlet flow rates of 0.677 m/s and 0.812 m/s, there was a large difference in weight loss, but the difference became much less for the flow rates of 0.812 m/s and 0.947 m/s. Although the corrosion rate was found to increase with the increasing flow rate, the magnitude of the increase tended to decrease due to the barrier formed corrosion. The visually notable areas of corrosion (red circles in Figure 3) were observed further through the electron microscope scanning. The samples were observed further through the electron microscope scanning (SEM). Figure 4 shows the SEM pictures (with corrosion products) of these similar positions for three groups of samples: front view in Figures 4(a)–(c) and back view in Figures 4(d)–(f). For the inlet flow rate of 0.677 m/s, the sample surfaces are uneven with corrosive morphology of silt-shape [see the box in the Figure 4(a) and 4(d)], compared to the relatively smooth surfaces for the inlet flow rate of 0.812 m/s although clearly raised corrosion products Table 3. Corrosion Rate Measured from Sample Weight Loss in Different Flow Rate. Flow Rate cm–2 ΔW (mg P (mmy–1) d–1) 0.677 0.812 0.947 1.91 0.89 3.08 1.43 3.45 1.60 are also apparent (see the box in the Figure 4(b)] with even crater-like and crack-like corrosion [see the arrow in Figure 4(e)]. For the inlet flow rate of 0.947 m/s, sample surfaces are more even but with much significant increases of raised corrosion products with the shapes similar as craters [see the arrows in Figures 4(c) and 4(f)]. Figure 5 shows the morphology pictures after removing the corrosion product films: Figures 5(a)–(c) for the front view and Figures 5(d)–(f) for the back view. Uneven surfaces with larger corrosion pit area shallower depth are clearly shown in Figure 5(a), whilst corrosion pit area in Figure 5(b) was smaller but much deeper with lots of cellular corrosion pitting shown by the arrow [Figure 5(b)]. The corroded region in Figure 5(c) has the maximum number of pits that have the minimum pit areas and the deepest pit depth [the corrosion morphology characterization in Figures 5(d)–(f)]. 3.2. CFD Simulation 3.2.1. The Influence of Flow Rate to Distribution of Flow Field CFD simulation was performed to further investigate the differences in erosion corrosion at different flow rates of the samples. Figure 6 shows the flow field characteristics of the turbulent kinetic energy intensity and the boundary shear stress: Figure 6(a) for the cross-sectional view and Figure 6(b) for the front view. The distribution of flow field was not affected significantly by the increasing flow rate, however, the speed at same place was all boosted. Figure 6(c) shows that the turbulent kinetic energy of sample surface increases dramatically with the increasing flow rate. Figure 6(d) clearly shows that the increasing flow rate results in increasing stress intensity and its distribution trend, indicating the extension area of higher stress density. 3.2.2. The Effect of Corrosion Pitting on Distribution of Flow Field Figure 3. Macro corrosion morphology at different flow rates. (a) 0.677 m/s , (b) 0.812 m/s, (c) 0.947 m/s. Figure 7 displays the simulation results of the effects of corrosion pitting on the distribution of flow Experimental Study and Numerical Modelingof Erosion-corrosion of J55 Steel 239 Figure 4. Pictures of corrosion feature at different flow rate (front view): (a) 0.677 m/s , (b) 0.812 m/s, (c) 0.947 m/s; back view: (d) 0.677 m/s, (e) 0.812 m/s, (f) 0.947 m/s. field. Figures 7(a)–(b) present the flow rate distribution, showing that the fluid flow rate changes when passing through the pit. The fluid flow rate within the pit was near zero due to the influence of outer wall surface of pit. The flow rate was lower in certain areas of the pit upstream. For the inlet velocity of 0.677 m/s, the average flow rate near wall surface of corrosion pitting was about 0.759 m/s. As shown in arrow of Figure 8(a), the near-wall fluid flow rate of the corrosion pitting was the maximum about 1.33 m/s. The near-wall velocity far from the corrosion pitting was only about 0.475 m/s (as shown in the circle of the Figure 5. Pictures of sample surface without corrosion product layer at different flow rates (front view): (a) 0.677 m/s , (b) 0.812 m/s, (c) 0.947 m/s; back view: (d) 0.677 m/s, (e) 0.812 m/s, (f) 0.947 m/s. 240 D. Zhao, Z. Sun, Y. Zhao, X. Lü and X. Tan Figure 6. The whole CFD simulation. (a), (b): The distribution of rate, (c): turbulent kinetic energy, (d): wall shear stress). figure). With the increasing of flow rate, the distribution of flow field changed little and only flow rate in relevant position increases. Similar phenomenon was observed in other samples. The simulation findings show that the existence of corrosion pitting increased the turbulent kinetic energy and wall surface shear strength in the near-wall region of the corrosion pitting, as shown in Figures 7(c)–(d). In addition, the turbulent kinetic energy surrounding corrosion pitting was two times of that of corrosion pitting. However, the wall surface shear force surrounding the corrosion pitting increased dramatically, about 10 times larger than that of corrosion pitting. Many corrosion pitting existed in the area shown in Figure 7 and the corrosion product film surrounding the corrosion pitting showed irregular grooving or silt-shaped corrosion morphology. These findings are consistent with others from previous reports, for example [8]. Experimental Study and Numerical Modelingof Erosion-corrosion of J55 Steel 4. DISCUSSION 4.1. Corrosion Behavior It is well known that local fluid hydrodynamics plays an important role in erosion corrosion reactions 241 regarding the movement, distribution and diffusion of fluids [20]. The increasing flow rate results in the growth of local flow intensity of turbulence and the wall shear stress, which accelerates surface damages and causes the accelerated film detachment in corrosion products. When fresh sample surfaces, exposed to Figure 7. The CFD simulation of corrosion pitting (a), (b): The distribution of rate, (c): turbulent kinetic energy, (d): wall shear stress. 242 D. Zhao, Z. Sun, Y. Zhao, X. Lü and X. Tan the corrosive medium after corrosion products, were removed, there was a higher chance of the formation of different galvanic couples between the exposed sample surface and its contacted corrosion product, leading to accelerated corrosion in these areas. All these factors can cause higher weight loss and faster corrosion rate under higher flow rate. However, corrosion is an extremely complicated process that needs time to exert damaging effect. Although higher flowing rate increases corrosion rate, removes corrosion product layers and leads to an increased corrosion, the corrosion rate can decrease due to insufficient corrosion time. Because the flowing suspension contained no solid particles in this study, the strong erosion-corrosion effect was not observed clearly. For this reason, the maximal increase in corrosion rate was shown for the flow rate of 0.812 m/s other than the flow rate of 0.947 m/s. Moreover, the study suggests that the adsorbed C1– in the steel surface promoted the corrosion pitting [22]. C1– with strong electronegativity dissolved the part of the corrosion products of the iron and generated more flaws in the rust layer [Figure 4(e)]. A diffusion path of O2 then is provided for the corrosion to proceed. It is worth to note that higher flow rate can provide more sufficient Cl– and O2 for the reaction. When the corrosion started, the concentration of OH– ion appeared around the corrosion pitting, resulting in an anodic reaction that iron loses the electron. Because of the larger flow rate, the OH– generated outside of the corrosion pit was taken away by fluid while the OH– inside of the corrosion pit stayed. This caused corrosion pit extended to the interior, and the depth of the corrosion pit got deeper. Sufficient reaction between OH– and its surrounding iron elements at low flow rate leads to the corrosion pit extension trend to in adjacent area rather than towards in depth, which results in the different corrosion pit characteristics at high and low flow rate. 4.2. Simulation Study In the present study, weight loss and morphology feature show that there was considerable difference in the erosion-corrosion behavior at different flow rates of sample. High flow rate causes a large weight loss and penetration rate (Table 3). Mass transfer was also known to remove corrosion products from the metal surface [23]. Juan Wang et al. observed that more corrosion products were removed at higher wall shear stress values in the samples [24]. The differences in corrosion at various flows are due to the turbulent ki- netic energy and the wall shear stress determined by the flow rate of the medium. It is known that the fluid hydrodynamics is the important factor for erosion-corrosion behavior. CFD simulation indicates that there were large difference on the hydrodynamics at different locations of sample surface due to change of surface morphology [Figures (6)–(7)]. During the erosion corrosion test, the corrosion product film of the sample surface constantly shedding and produce, leading to the uneven surface of the sample. When the medium flows through the surface, changes in the turbulence intensity and the wall shear stress distribution differences associated with the flow field had a huge impact on the weight loss and corrosion rate of sample. High local shear stress causes corrosion product detachment and potentially strut fracture [25–28]. When the flow rate increases, the turbulent kinetic energy of fluid and surface shear force increase in the nearby area of corrosion pit. Therefore, the nearby product film bears higher outer stress and falls off, the new matrix surface is then exposed and the new corrosion product film is formed. This continuous process of the formation-falling off of the product film causes the nucleation and extension of the stress corrosion. This phenomenon is more significant when the fluid flow accelerates, see Figure 7. During erosion-corrosion process, fluid flow would accelerate the mass transfer process of cathodic reactants and products, and then accelerate the corrosion of steel [27]. At the same time, we observed that the increase of flow rate may accelerate the mass transfer process. In addition, as the fluid flow accelerates, the erosion intensity on the sample surface increases, which makes the loosen corrosion layer falls off more easily, which resulted in thinner corrosion layer [7,27]. Therefore, this morphology with corrosion pit makes the scouring environment more complicated. In addition, the comparison between the erosion-corrosion experiment and the CFD simulation shows that the existence of corrosion pit can easily cause the corrosion product film to fall off and to further intensify the corrosion. 5. CONCLUSIONS The following conclusions can be drawn from on the study of the erosion-corrosion of J55 steel under the local hydrodynamic conditions of Huanghe valley: 1. Within the range of flow rate (0.677 m/s, 0.812 m/s Experimental Study and Numerical Modelingof Erosion-corrosion of J55 Steel and 0.947 m/s.), the sample mass loss increases with the fluid flow rates, however, the magnitude of the increase tends to decrease, indicating that when the flow rate increases to a certain degree, its effect on corrosion becomes weaker. 2. For the flow rate of 0.647 m/s, the corrosion pit is shallower with larger area. For the flow rate of 0.947m/s, the corrosion pit is deeper with smaller area. 3. The corrosion pit and raised corrosion product film change the distribution of nearby fluid. CFD simulation shows that the boundary flow rate near to the sample with defect is seven times of the flow rate at smooth boundary. The fluid around sample surface has large turbulent kinetic energy and surface shear stress, which intensifies the corrosion. 4. The corrosion rate increases as the flow rate increases. 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