Evaluating the Impact of Redox Potential on the Corrosion of Q125, 316L, and C276 Steel in Low-Temperature Geothermal Systems
<p>Fluid 1 evolution and steel behavior from each Wheaton bottle containing a single piece of steel. (<b>A</b>,<b>B</b>) Fluid evolution. (<b>C</b>,<b>D</b>) Steel roughness and corrosion rate. The surface roughness values are averages of the entire ROI scan area and are taken from the Fluid 1 AFM data in <a href="#cmd-04-00030-t002" class="html-table">Table 2</a>. Surface roughness uncertainties are at the 1 σ level.</p> "> Figure 2
<p>Example of probable polishing relic from 316L TP3 from Fluid 1. Red areas represent topographic highs and blue areas represent topographic lows. (<b>A</b>) The transects 1 and 2 are both 30 µm in length. This is the diameter of the first diamond lapping film used in sample polishing. (<b>B</b>) Colorized version of the same ROI. (<b>C</b>) Oblique view with scale bar. Note the correlation between the transects and the deep linear valley, interpreted as a relic from the 30 µm diamond lapping film.</p> "> Figure 3
<p>Images of the selected region for AFM analysis on each steel sample before and after the full 1200 h exposure to Fluid 1. The “after exposure” samples are multiple images photomerged at the same magnification as the single “before exposure” image. The green stars refer to polishing relics. Green rectangles indicate the general ROI that was analyzed using AFM. Examples of AFM topographic maps from these areas are presented in <a href="#cmd-04-00030-f004" class="html-fig">Figure 4</a>. The red rectangle on Q125 from TP2 is an unpolished area and corresponds to the “u.p.” data row in Fluid 1 of <a href="#cmd-04-00030-t002" class="html-table">Table 2</a>. Photographs except for Q125 from TP3 illustrate both an oxidized rind and the inside of the same sample after rind removal. This is the surface used for AFM analysis (<a href="#cmd-04-00030-f004" class="html-fig">Figure 4</a>, <a href="#cmd-04-00030-t002" class="html-table">Table 2</a>). The interior surface is the surface that was analyzed using AFM.</p> "> Figure 4
<p>AFM height retrace topographic maps at each timepoint after exposure to Fluid 1. Red areas represent topographic highs and blue areas represent topographic lows. Note that the text below the AFM graphic is the average of each ROI for that piece of steel at the corresponding timepoint. Values at the 1σ level are given in parentheses. All AFM maps are shown using the same amount of scale exaggeration unless otherwise noted. (<b>A</b>) TP1. (<b>B</b>) TP2. (<b>C</b>) TP3. The scale exaggeration for the Q125 AFM topographic map has been reduced by a factor of 1.9 to reduce noise.</p> "> Figure 5
<p>Fluid 2 evolution and steel behavior from each Wheaton bottle containing a single piece of steel. (<b>A</b>,<b>B</b>) Fluid evolution. (<b>C</b>,<b>D</b>) Steel roughness and corrosion rate. Note that, for example, 1E-07 cm/hr is equivalent to 1 × 10<sup>−7</sup> cm/hr. The surface roughness values are averages of the entire ROI scan area. The surface roughness values are averages of the entire ROI scan area and are taken from the AFM Fluid 2 data in <a href="#cmd-04-00030-t002" class="html-table">Table 2</a>. Surface roughness uncertainties are at the 1 σ level.</p> "> Figure 6
<p>Photomerge images of the selected region for AFM analysis on each steel sample before and after the entire 1200 h exposure to Fluid 2. Both “before exposure” and “after exposure” images were taken at the same level of magnification. The green stars refer to polishing relics. Green rectangles indicate the general ROI that was analyzed using AFM (<a href="#cmd-04-00030-f007" class="html-fig">Figure 7</a>). The red rectangle is a specific location referenced in the text and the corresponding AFM map is found in <a href="#cmd-04-00030-f007" class="html-fig">Figure 7</a>C. Photographs except for Q125 from TP3 illustrate an oxidized rind and the inside of the same sample after rind removal.</p> "> Figure 7
<p>AFM height retrace topographic maps at each timepoint after exposure to Fluid 2. Red areas represent topographic highs and blue areas represent topographic lows. Note that the text below the AFM graphic is the average of each ROI for that piece of steel at the corresponding timepoint. Values at the 1σ level are given in parentheses. All images are shown using the same amount of scale exaggeration unless otherwise noted. (<b>A</b>) TP1. (<b>B</b>) TP2. (<b>C</b>) TP3. Regarding Q125, the scale exaggeration for this AFM topographic map has been reduced by a factor of 1.9 to reduce noise. The red box outlining the C276 AFM map corresponds to the same ROI outlined in <a href="#cmd-04-00030-f006" class="html-fig">Figure 6</a>.</p> "> Figure 8
<p>Redepositional features on steel surfaces. (<b>A</b>) Spire structure on C276 steel after TP3-ROI, outlined with a box. (<b>B</b>) Pitting corrosion pit with immediately adjacent redepositional rim on 316L TP3. Amorphous elevated structures are highly spatially correlated with phase retrace—ROI outlined in black.</p> "> Figure 9
<p>AFM topographic maps from Q125 TP2 after exposure to Fluid 1 (n = 6) comparing the surface roughness values obtained from the ROP and SOP window models. The spatial resolution is within 0.2 μm of the reported coordinates. (<b>A</b>) ROP results with ten square sub-windows within the full 90 × 90 μm window. (<b>B</b>) SOP results with four square sub-windows within the full 90 × 90 μm window. (<b>A1</b>,<b>B1</b>) Surface roughness obtained from each sub-window (numbered datapoints denoted by red triangles correspond to the respective sub-window in (<b>A</b>,<b>B</b>)). The remaining datapoints denoted by circles are the surface roughness values from additional AFM topographic maps of Q125 from TP2 after exposure to the low-Eh fluid. The black bar represents the 1σ of the full maps at the 50 × 50 μm scale (<span class="html-italic">n</span> = 2) and the 90 × 90 μm scale (<span class="html-italic">n</span> = 4), and is centered about the mean.</p> "> Figure 10
<p>Log–log analysis of scan area window size versus surface roughness for both ROP and SOP models. All data are AFM results obtained after exposure to Fluid 1. Each trendline pertains to all datapoints (independent of time). (<b>A</b>) Q125 steel. (<b>B</b>) 316L steel. (<b>C</b>) C276 steel.</p> ">
Abstract
:1. Introduction
2. Materials and Methods
2.1. Steel and Fluid Preparation
2.2. Exposure Testing
2.3. Atomic Force Microscopy
3. Results
3.1. Fluid 1 (Low Eh) Exposure
3.2. Fluid 2 (High Eh) Exposure
4. Discussion
4.1. Steel Grade Comparison
4.2. Fluid Comparison
4.3. Redepositional Features
4.4. Data Validation: Scale Dependence and Scan Window Model Selection
5. Conclusions
- The AFM results show that Q125 performs approximately the same when exposed to both fluids and experiences general corrosion. After 1200 h of exposure, Q125, upon exposure to the reducing Fluid 1 solution, produced a weathering rind at a rate of 0.29% of the mass of the initial sample. Exposure to the oxidizing Fluid 2 solution produced a weathering rind at a rate of 0.74 wt % of the mass of the initial sample. Both the 316L and C276 steels performed similarly to each other, as both became progressively rougher over time when exposed to both corroding fluids. Pitting corrosion is the predominant form found on the surfaces of 316L and C276. The concentration of sulfur present in the fluids may be derived from steel dissolution. It is unknown if this is a contributing factor to the observed pitting corrosion or what the sulfur concentration (present as thiosulfate (e.g., [32])) must be for initiation. The pH and Eh of the initially reducing Fluid 1 change minimally after 1200 h, indicating that it is approaching atmospheric equilibrium at that point. Conversely, and perhaps perplexingly, after 1200 h, the pH of the initially oxidizing Fluid 2 evolves to become strongly basic and has a comparatively low Eh. This may be at least partially caused by H2O2 decay and the subsequent consumption of H+, followed by H2 production. Finally, our results have shown that significant steel corrosion can occur even after exposure to very low-ionic-strength (<0.0005 M) fluids.
- Redepositional peaks exhibit a significant spatial correlation with pitting corrosion, highlighting the utility of combining height retrace and phase retrace AFM maps. In qualitative terms, redepositional features are observed to have a lower phase retrace angle than the substrate’s bulk or approximate average angle. The accurate identification of these corrosion deposits could provide insights for selecting an appropriate antiscalant. AFM offers the advantage of providing ultra-high-resolution corrosion analysis.
- Although the surface features may appear heterogeneous, there seems to be no significant influence of sample site selection bias. Two models were created to examine the log–log relationship between the surface roughness and window scan area. Neither model exhibited a substantial correlation between these variables over approximately three log units, indicating a lack of scale sensitivity within this range. The specific spatial extent to which this observation no longer holds true remains unknown, and further research in this area will likely yield interesting results.
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Steel Name AISI/EN/API | Purpose/Use | Elemental wt % | M g/mol | Ionic Charge | |||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
C | Co | Cr | Cu | Fe | Mn | Mo | N | Ni | P | S | Si | V | W | ||||
C276/2.4819/- | Heat exchangers [23] and pump shafts [24] | 0.006 | 0.01 | 15.6 | 0.02 | 5.7 | 0.52 | 16.2 | - | 58 | 0.003 | 0.001 | 0.05 | 0.01 | 3.67 | 67.9 | 2.8 |
316L/1.4404/- | Condensers [25] and heat exchangers [23] | 0.02 | - | 16.7 | 0.55 | 68.5 | 1.67 | 2.03 | 0.0533 | 10.1 | 0.027 | 0.027 2 | 0.4 | - | - | 56.2 | 2.1 |
-/-/Q125 | High strength/pressure casing [26,27] | 0.35 | - | 1.5 | - | 94.9 | 1.35 | 0.85 | - | 0.99 | 0.02 | 0.01 | - | - | - | 56.0 | 2.0 |
At TP0: pH = 7 T = 75 °C | TP0 | TP1 | TP2 | TP3 | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Time: 0 h | Time: 24 h, Elapsed Time: 24 h | Time: 168 h, Elapsed Time: 192 h | Time: 1008 h, Elapsed Time: 1200 h | |||||||||
Average Surface Rough. 1σ (nm) | Average Trans. 1σ (nm) | Average Surface Rough. 1σ (nm) | Average Trans. 1σ (nm) | Corr. Rate (mm/y) | Average Surface Rough. 1σ (nm) | Average Trans. 1σ (nm) | Corr. Rate (mm/y) | Average Surface Rough. 1σ (nm) | Average Trans. 1σ (nm) | Corr. Rate (mm/y) | ||
Standard Deviations are Reported at the 1σ Level and Pertain Values Inside Parentheses | ||||||||||||
Fluid 1 | Q125 | 30 (4) | 400 (43) | 29 (8) | 510 (159) | 8.2 × 10−3 | 36 (10) | 972 (301) | 0.051 | 366 (148) | 6286 (2428) | 0.11 |
Q125 (u.p.) | 135 | 1649 | - | - | - | ~1352 | >15,197 | - | - | - | - | |
316L | 17 (32) | 415 (282) | 55 (39) | 1296 (746) | 8.8 × 10−3 | 75 (44) | 1204 (833) | <LOD | 101 (126) | 1824 (901) | <LOD | |
C276 | 23 (15) | 617 (160) | 17 (17) | 424 (370) | <LOD | 34 (19) | 1003 (435) | <LOD | 81 (88) | 1477 (1092) | <LOD | |
Fluid 2 | Q125 | 17 (11) | 748 (312) | 27 (30) | 1003 (523) | 1.1 × 10−2 | 21 (20) | 652 (593) | 8.1 × 10−4 | 582 (338) | 6864 (2724) | 0.13 |
316L | 15 (6) | 466 (84) | 20 (10) | 562 (239) | 1.8 × 10−2 | 16 (13) | 687 (397) | <LOD | 30 (20) | 696 (369) | 8.6 × 10−4 | |
C276 | 15 (8) | 337 (216) | 15 (13) | 475 (255) | 8.7 × 10−3 | 18 (6) | 508 (120) | 1.8 × 10−3 | 33 (32) | 1085 (1521) | 3.1 × 10−4 |
Log–Log Analysis after Fluid 1 Exposure | ROP Range log(Sa) (µm) | ROP Range log(Scan Area) (µm2) | SOP Range log(Sa) (µm) | SOP Range log(Scan Area) (µm2) |
---|---|---|---|---|
Q125 TP1 | 0.581 | 2.000 | 0.581 | 1.204 |
Q125 TP2 | 0.358 | 2.511 | 0.692 | 1.556 |
Q125 TP3 | 0.852 | 2.511 | 1.067 | 1.556 |
316L TP1 | 1.369 | 2.511 | 1.288 | 1.556 |
316L TP2 | 1.196 | 2.511 | 1.546 | 1.556 |
316L TP3 | 1.634 | 2.511 | 1.328 | 1.556 |
C276 TP1 | 1.080 | 2.000 | 0.961 | 1.204 |
C276 TP2 | 1.619 | 2.511 | 1.639 | 1.556 |
C276 TP3 | 1.454 | 2.511 | 1.577 | 1.556 |
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Bowman, S.; Agrawal, V.; Sharma, S. Evaluating the Impact of Redox Potential on the Corrosion of Q125, 316L, and C276 Steel in Low-Temperature Geothermal Systems. Corros. Mater. Degrad. 2023, 4, 573-593. https://doi.org/10.3390/cmd4040030
Bowman S, Agrawal V, Sharma S. Evaluating the Impact of Redox Potential on the Corrosion of Q125, 316L, and C276 Steel in Low-Temperature Geothermal Systems. Corrosion and Materials Degradation. 2023; 4(4):573-593. https://doi.org/10.3390/cmd4040030
Chicago/Turabian StyleBowman, Samuel, Vikas Agrawal, and Shikha Sharma. 2023. "Evaluating the Impact of Redox Potential on the Corrosion of Q125, 316L, and C276 Steel in Low-Temperature Geothermal Systems" Corrosion and Materials Degradation 4, no. 4: 573-593. https://doi.org/10.3390/cmd4040030