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Hong-mei Zhang, Yan Li, Ling Yan, Fang-fang Ai, Yang-yang Zhu, and Zheng-yi Jiang, Effect of large load on the wear and corrosion behavior of high-strength EH47 hull steel in 3.5wt% NaCl solution with sand, Int. J. Miner. Metall. Mater., 27(2020), No. 11, pp.1525-1535. https://dx.doi.org/10.1007/s12613-020-1978-3
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To simulate the wear and corrosion behavior of high-strength EH47 hull steel in a complicated marine environment in which seawater, sea ice, and sea sand coexist, accelerated wear and corrosion tests were performed in a laboratory setting using a tribometer. The effect of large loads on the behavior of abrasion and corrosion in a 3.5wt% NaCl solution with ice and sand to simulate a marine environment were investigated. The experimental results showed that the coefficient of friction (COF) decreases with increasing working load; meanwhile, the loading force and sand on the disk strongly influence the COF. The mechanisms of friction and the coupling effect of abrasion and corrosion in the 3.5wt% NaCl solution with sand were the wear and corrosion mechanisms; furthermore, the wear mechanism exerted the predominant effect.
Marine equipment and marine engineering steel are adversely affected by prolonged exposure to wind, waves, sea currents, sediment, and sea ice in marine environments. Therefore, erosion, corrosion, and wear in the extreme marine environment result in coupled tribological behavior comprising corrosion behavior, electrochemical corrosion behavior, and erosion behavior [1–5]. The combined corrosion and wear behavior of materials differs substantially from that of corrosion and wear acting independently; it is not a mathematical superposition of corrosion alone or wear alone, but a complex interaction.
In the corrosive medium, the metal surface will form a surface film whose properties differ from those of the matrix; this film can be weakened or even cracked by a friction force or particle impact [6–8]. Wear will cause thinning of or damage to the passivation film, exposing the material surface to the solution. Stirring the solution accelerates the diffusion of corrosion products (metal ions). Surface dislocations, vacancies, and other defects are increased by shear force on the surface of the material, and increasing the surface activity leads to an increase of the metal corrosion speed [9–11].
The corrosion layer on the material surface is loose and porous. It can be easily washed away, increasing the loss of material and the roughness of the metal surface, damaging the integrity of the materials, reducing the binding strength, and aggravating the wear [12–16].
Other researchers have reported experiments in which wear, the coefficient of friction (COF), and wear rate under the condition of the coupled action of corrosion and wear were found to be lower than those under the same test conditions with dry wear [17–18]. Several scholars have investigated the corrosion and wear of metal materials, including the damage and repair of the metal surface film, the interaction between corrosion and wear, and the mechanisms of corrosion and wear [19–23].
Watson et al. [15] summarized previously reported research results on the corrosion and wear interaction of metal materials. A series of reports showed that the surface of carbon steel cannot form a stable blunt corrosion film under oceanic conditions; it instead forms a loose rust layer, which provides little protection from further corrosion [24–26]. During abrasion tests, the rust layer formed on the material surface was quickly removed, resulting in a failure of the protective film in the abrasion area and the interaction between corrosion and wear [27–30].
The analysis of the interaction between corrosion and wear of 304 stainless steel indicated that the friction and wear process promote macroscopic galvanic corrosion and aggravate the corrosion tendency of materials [31]. Bateni et al. [32] compared the friction and wear performance of 304 stainless steel under dry friction and artificial seawater qconditions. Their results showed that the wear of stainless steel under dry friction was greater than that in NaCl solution. Wu et al. [33] investigated the tribological behavior of Babbitt alloy 16-16-2 and aluminum bronze ZCuAl9Mn2 in a seawater environment. They reported that the COF increased with increasing load and then remained relatively stable, whereas it decreased with increasing rotation speed.
In the present work, to simulate the corrosion and abrasion behavior of high-strength EH47 hull steel in a complicated marine environment where seawater, sea ice, and sea sand coexist, accelerated wear and corrosion tests were performed in a laboratory setting using a tribometer. The tribological tests were conducted using a ball-on-disk tribometer with Si3N4 against high-strength EH47 hull steel at low temperatures, with large loads of 50, 100, 200, and 300 N with sand and 50 and 100 N without sand. The disks were continuously immersed in 3.5wt% NaCl solution with ice and sand during the entirety of the tribological tests.
A low-carbon micro-alloyed high-strength hull steel, EH47, used on ships, was used as the disk material in this study. The chemical compositions of the experimental material were 0.07wt% C, 0.20wt% Si, 1.42wt% Mn, 0.006wt% P, 0.001wt% S, 0.07wt% Cr, 0.79wt% Ni, 0.22wt% Mo, 0.04wt% Nb, 0.006wt% V, 0.013wt% Ti, and 0.03wt% Al, with the balance composed of Fe.
The average hardness of the EH47 was HV 208, its yield strength and tensile strength were 390 and 600–690 MPa respectively, and its elongation was 20%.
All the disks for the ball-on-disk tests were machined to 46 mm in diameter and 6 mm in thickness. The ball specimen was a 10 mm diameter Si3N4 ceramic ball (HV 0.5, 1800 kg/mm2, modulus of elasticity E = 210 GPa, roughness Ra = 0.02 μm). The samples and balls were cleaned with alcohol and acetone, and then dried immediately before the test. The as-received surface morphologies and 3D (three dimensional) profiles of the disk are shown in Figs. 1(a) and 1(b).
An Rtec MFT-5000 multifunctional tribometer was used to measure the COF values with ball-on-disk tribological tests. The disk and the Si3N4 ceramic ball were cleaned with ethanol and then assembled prior to the tests. All of the disks were immersed into a 3.5wt% NaCl solution with 5wt% sand at 0°C (salt water with ice) continuously during the entirety of the tribological tests. The wear tests were carried out under different loading-force and sliding-time conditions, and each test was repeated three times to obtain a mean COF value.
The COF and wear rate of EH47 high-strength ship steel were measured with a tribometer. The disks and balls were cleaned after the tribological tests in an ultrasonic acetone bath, and the 3D profile of wear tracks on the disks and balls were observed with a KEYENCE VK-5000 3D laser scanning microscope. The micrographs and surface composition of the abrasion scar surfaces were evaluated by scanning electron microscopy (SEM, Zeiss-Sigma, Germany) and by energy-dispersive spectroscopy (EDS) microanalysis.
After the wear experiments, corrosion experiments were carried out at room temperature by immersing the samples in a container for 7 d. The container was filled with 3.5wt% NaCl solution and 5wt% silica sand with a mean size of 250 μm.
All electrochemical tests were carried out in seawater at room temperature. The test samples were EH47 steel under different wear conditions. The electrochemical measurements were performed using a CHI760E electrochemical workstation produced by Shanghai ChenHua Instrument Co., Ltd. The scanning speed of the polarization curve test was 0.5 mV/s, and the scanning range was −200 to 200 mV relative to the open-circuit potential. The frequency range of the electrochemical ac impedance was 0.1–10 MHz, and the voltage amplitude was 10 mV.
The effect of large loads on the tribological behavior of high-strength EH47 hull steel was investigated using a tribometer in a laboratory. The tribocorrosion tests were performed with the disks immersed in a 3.5% NaCl solution with ice and sand under loads of 300, 200, 100, and 50 N and under loads of 100 and 50 N with ice and no sand. The COF values measured under two different conditions are shown in Figs. 2(a) and 2(b). The in situ curves of the COF as a function of time show a similar pattern when the loading force is greater than 100 N with sand, and the COF exhibits two stages throughout the whole friction process. The high COF was caused by severe plowing because the ball is much harder than the disk. During the initial stage of the test, the sand and large loading force resulted in a distinct fluctuation, corresponding to a large COF between the ball and disk. The COF then reached a steady friction state, where the ball slid on the uniform worn track. In particular, the curve of the COF obtained under a 50 N loading force (with and without sand) differs slightly from the curve obtained with a loading force greater than 100 N. The curves of the COF show a stable and similar variation trend, and the average COF values under 50 and 100 N of loading force are 0.32 and 0.35, respectively, as shown in Fig. 2(b). The COF clearly increases with increasing working load. The loading force and sand on the disk influence the COF; therefore, the smallest value was obtained under at load of 50 N without sand. Two reasons can explain this trend. First, the volume of water that flowed into the disk grooves decreased under higher loads, which in turn increased the real contact surface between the disk and ball. Second, sand particles that entered the disk grooves played no significant role under the lower loading conditions during abrasion.
Fig. 3 shows the corresponding 3D profiles of the tracks worn on disks after the tribological tests. The tests were performed under loads of 300, 200, 100, and 50 N with ice and sand and under loads of 100 and 50 N with ice and no sand. The width (y axis) and height (x axis) of the wear track increased with increasing loading force. The worn track under a load of 300 N became wider and deeper, corresponding to the largest COF, as shown in Fig. 2(a); however, the worn surface of the disk showed smooth areas instead of plowing grooves, as shown in Fig. 3(a). The worn tracks of the disk surface under 100 and 200 N of force were grooved and plowed substantially, and the plowing grooves on the worn surface were parallel to the sliding direction, as shown in Figs. 3(b) and 3(c). With an increase of the loading force, the grooves on the worn surface became deeper in the sliding direction, as shown in Figs. 3(b)–3(d), with the exception of the loading force of 300 N (Fig. 3(a)). The wear behaviors with sand were completely different than those without sand, consistent with the previously measured COF values and with the results in Fig. 2.
Fig. 4 shows the SEM micrographs of tracks worn under different loading conditions. The tests were performed under loads of 300, 200, 100, and 50 N, as well as under loads of 100 and 50 N with ice and no sand. All of the disks were submerged in salt water with ice and sand during the entirety of the tribological tests. The scratches in the worn tracks on the surface became deeper with increasing load. The presence of plowing grooves on the worn surface in the direction of sliding is a dominant feature (Figs. 4(b)–4(d)), with the exception of the loading force of 300 N (Fig. 4(a)). However, no adhesion phenomenon is evident under a loading force of 200 or 100 N. In particular, the worn surface of the disks appears to be smooth, with slight abrasion and plowing grooves under the loading force of 300 N, as shown in Fig. 4(a). Furthermore, adhesion is a dominant feature on the worn surface of the disk subjected to a loading force of 300 N, resulting in a high COF in Fig. 2(a). Under the lower loading force without sand, the abrasion is slight and the COF is smaller because of a lack of abrasion wear compared with the case of a lower loading with sand.
Fig. 5 shows SEM micrographs of wear scars on the disk surface under different conditions. The sliding grooves of the wear scar on the disk surface are deeper in the sliding direction. The adhesive area and abrasion scars are more evident and larger with the loading force of 300 N, as shown in the SEM image in Fig. 5(a); however, fewer microvoids and microcracks are observed because the amount of salt water with sand between the sliding grooves of the disk and ball decreases with a high loading force between the contact surface of the ball and disk. This decrease in the amount of salt water with sand substantially increases the friction and wear and adversely influences the ball-bearing effect between the ball and disk. Furthermore, the dominant wear mechanisms are the abrasive wear mechanism and the adhesion wear mechanism under high loading forces, and the fatigue wear mechanism does not substantially influence the wear mechanism.
While the wear scars of the disk surface under 200 and 100 N of loading force were severely plowed, microvoids and isolated pits were much larger than those observed under other loads, consistent with the COF results in Figs. 2(a) and 2(b). The primary wear mechanism is abrasion because the action of sand particles and plowing dominates the whole abrasion process, which leads to high friction and wear during the ball-on-disk test under a high loading force. Meanwhile, the microvoids and isolated pits indicate that surface fatigue strongly influences the wear of the disk. Therefore, the wear mechanisms are the abrasive wear mechanism and the fatigue wear mechanism at relatively high loadings such as at 200 and 100 N, as shown in Figs. 5(b)–5(d). However, the adhesive effect between the disk surface and ball only slightly influences the wear mechanism.
In particular, the worn disk surface exhibited slight abrasion and fewer pits and microvoids were observed on the worn disk under a lower loading force of 50 N (Figs. 5(e) and 5(f)). The loading force plays an important role in the friction and wear behavior because the amount of salt water with sand between the contact surface of the ball and disk changes dramatically with loading force. These changes will affect the friction and wear substantially and will further influence the ball-bearing effect between the ball and disk.
Fig. 6 shows the corrosion product morphology of the worn track after 7 d of the specimen being immersed in 3.5wt% NaCl solution. Figs. 6(a)–6(c) indicate that the corrosion rust layer on the worn tracks of the disk is a loose structure of a block cluster. Figs. 6(d) and 6(e) shows two types of corrosion products on the worn tracks of the disk: one like block clusters and another with a needle-and-sheet appearance. Fig. 6(f) shows that the corrosion products on the worn tracks of the disk are denser and exhibit the block and layer structure. Other authors [34] have noted that the continuous compact needle or sheet formed under the outer rust layer is the most stable corrosion product and can effectively prevent further corrosion of the matrix.
Even if the corrosion products cover the disk surface of the worn track, the salt water can still contact the disk surface through the microcracks between the corrosion products, eventually causing the rust layer to fall off. After loose corrosion products fall off, they cannot prevent further corrosion of the surface of the sample; the rust layer will then be reformed on the sample surface [26–27]. In addition, the wear action between the ship hull surface and seawater sand can easily remove the corrosion products of the contact surface of the steel and expose a fresh metal surface, thereby further accelerating corrosion [29–30].
Figs. 7(a) and 7(b) show the corrosion product morphology and EDS analysis results of the worn track after 7 d of immersion in 3.5wt% NaCl solution. The corresponding EDS analysis results revealed the presence of C, O, Na, Mg, Si, S, Cl, and Fe at point A in Fig. 7(a) and C, O, Na, Si, Mo, Cl, and Fe at point B in Fig. 7(b). The results show that the poor Mo area and the rich Mo area are represented by point A in the matrix and point B in Fe–Mo oxides, respectively. In Fig. 7(b), the Mo content at point B is 1wt%; by comparison, no Mo is observed at point A in Fig. 7(a), but the Fe and O contents are high, indicating that it is Fe oxide.
Fig. 8 shows an SEM image and EDS analysis results for the cross section of worn track after 7 d of immersion in 3.5wt% NaCl solution under a loading force of 300 N. It indicates that the distributions of Fe, Na, and Mn are homogeneous. However, as evident from Fig. 8, the O, which is the main element combined with Fe, is mainly clustered in the grooves, indicating that wear strongly influences iron oxidation. The main corrosive element in the environment, Cl, exhibits obvious segregation in the groove. In the corrosion process, Cl, as the most important corrosive element, functions as a catalyst. Balusamy and Nishimura [35] as well as other authors [36–37] have suggested that higher Cl-ion concentrations results in the formation of a larger amount of porous β-FeOOH in the corrosion products. The greater proportion of such a porous structure in the corrosive medium and the exchange of oxygen in the environment provide a transmission channel, accelerating the corrosion of the metal. This effects especially promotes early corrosion of the metal. Some researchers have reported that the corrosion products expected in a NaCl solution are chloride green rust (i.e., Fe4(OH)8Cl·2H2O), Fe3O4, Fe2O3, and Fe(III) oxyhydroxides, mainly γ-FeOOH [38–40]. Fe(OH)2 can form, whereas Fe(OH)3 does not form (FeOOH phases are substantially more stable).
The electrochemical corrosion process can be analyzed through measurement of polarization curves. Fig. 9(a) shows the polarization curve of the worn surface of the EH47 steel disk sample fully immersed in seawater for 0 d under low load (without sand). No significant difference is observed in the polarization curve of the worn surface of EH47 steel samples under loads of 50 and 100 N. The anode curve shows obvious passivation characteristics, and the passivation zone is ~0.7 V, starting from −0.9 V into the passivation zone and ending at −0.2 V.
Table 1 shows the results of fitting the polarization curve of the worn surface of the EH47 steel disk sample fully immersed in seawater for 0 d under low load (without sand). According to the data in Table 1, the minimum corrosion current density (Icorr) on the wear surface of the EH47 steel sample was 2.294 × 10−5 A/cm2 when the load was 50 N; this specimen exhibited a lower corrosion rate and better corrosion resistance than that subjected to a load of 100 N. These results indicate that a large load can accelerate corrosion of the wear surface of the EH47 steel sample.
| Load | βa / (V·dec–1) | βc / (V·dec–1) | Ecorr / V vs. SCE | Icorr / (A·cm–2) |
| 100 | 3.794 | 6.521 | −0.966 | 2.731 × 10−5 |
| 50 | 3.569 | 6.059 | −0.976 | 2.294 × 10−5 |
| Note: βa——Anodic Tafel constants, βc——Cathodic Tafel constants, Ecorr——Corrosion potential. | ||||
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Fig. 10 shows the Nyquist impedance spectra of the worn surface of the EH47 steel disk sample immersed in seawater for 0 d under low load (without sand). As evident from the figure, the Nyquist plot shows an obvious capacitive arc, all of which are complete semicircles. The arc radius and impedance of the EH47 steel sample subjected to a load of 50 N are larger than those of the sample subjected to a load of 100 N, and the corrosion rate is lower than that of the sample subjected to 100 N, consistent with the polarization curves.
Fig. 11 shows that the material spontaneously forms a macroscopic galvanic corrosion system and that electrons flow from the anode to the cathode during the corrosion process, resulting in oxygen adsorbed onto the surface of the steel being reduced and forming OH−. The wear process subsequently promotes the formation of OH− at the interface between the electrochemical anode and seawater, and the OH− reacts with Fe2+ to form Fe(OH)2. The unstable Fe(OH)2 easily reacts with O2 to form stable Fe(OH)3, which is a reddish-brown powder with low bonding strength to steel substrates. It does not form a dense corrosion film to protect the metal substrate.
The wear and corrosion mechanism in 3.5wt% NaCl solution with sand between the contact surface of the ball and the EH47 steel disk under a high loading force is explained in Fig. 11. The worn scar and deep groove are caused by the large loading force. In the first stage, the dominant wear mechanisms were the abrasive wear mechanism and the adhesion wear mechanism under the large loading force. In this stage, the saltwater could enter the contact surface between the worn track and the ball through microcracks and pores of the rust layer (which may finally peel off). However, the corrosion products on the contact surface of the steel can be removed easily by the wear action between the ship hull surface and seawater, resulting in exposure of a fresh metal surface and further accelerating corrosion. Thus, the experimental results show that the wear mechanism was the predominant wear and corrosion mechanism. Although the impact of corrosion was light, the corrosion could still occur under abrasion friction, which exposes fresh surfaces and accelerates wear.
(1) The experimental results showed that the loading force strongly affected the COF and the depth and width of worn scars. The scar depth and width on the disk increased substantially with increasing loading force, with the exception of the loading force of 300 N.
(2) The dominant wear mechanisms were the abrasive wear mechanism and adhesion wear mechanism under high-loading-force conditions, and the fatigue wear mechanism did not substantially influence the wear mechanisms. The wear mechanisms at relatively high loadings were the abrasive wear mechanism and fatigue wear.
(3) The experimental results showed that the behavior of friction and the coupling effect of corrosion and abrasion in the complicated marine environment were the wear and corrosion mechanism; furthermore, the wear mechanism exerted the predominant effect. Although the contribution of corrosion components was slight, corrosion could occur under the abrasion friction, which exposes fresh surfaces and accelerates wear. The wear action between the ship hull surface and the seawater sand could easily remove the corrosion products of the contact surface of the steel and expose the fresh metal surface, thereby further accelerating corrosion.
(4) According to polarization curves of the worn surface of EH47 steel disks, a large load can accelerate the corrosion of the worn surface of EH47 steel.
This work was financially supported by the National Natural Science Foundation of China (Nos. 51474127 and 51671100) and the State Key Laboratory of Metal Material for Marine Equipment and Application-University of Science and Technology Liaoning co-project, China (Nos. SKLMEA-USTL 2017010 and 201905).
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