Acta Metallurgica Sinica (English Letters) ›› 2019, Vol. 32 ›› Issue (4): 506-516.DOI: 10.1007/s40195-018-0760-2
Special Issue: 2019年腐蚀专辑-1
• Orginal Article • Previous Articles Next Articles
Canshuai Liu1,2, Jianqiu Wang1(), Zhiming Zhang1, En-Hou Han1, Wei Liu3, Dong Liang3, Zhongtian Yang3
Received:
2018-03-22
Revised:
2018-04-25
Online:
2019-04-10
Published:
2019-04-19
Contact:
Wang Jianqiu
About author:
Dr. Kun-Kun Deng was born in 1983 and was awarded Ph. D in Harbin University of Technology in 2011. After graduation, he worked in the College of Materials Science and Engineering, Taiyuan University of Technology. At the same time, he continued his research work on the design, fabrication and processing of advanced Mg-based material in. Now, he is the vice chairman of Youth Committee in Magnesium Alloy Branch of Chinese Materials Research Society. He was denoted as young academic pacemaker of Shanxi Province in 2018. He has held two projects of National Nature Science Foundation of China, one project of Specialized Research Fund for the Doctoral Program of Higher Education, one Project of International Cooperation in Shanxi and two projects of Natural Science Foundation of Shanxi. He has published more than 60 articles. The time cited is more than 840 (without selfcitations), and the H-index is 22. In addition, he has published one academic monograph and acquired eight Chinese patents.
Canshuai Liu, Jianqiu Wang, Zhiming Zhang, En-Hou Han, Wei Liu, Dong Liang, Zhongtian Yang. Characterization of Corrosion Behavior of Irradiated X65 Low Carbon Steel in Aerobic and Unsaturated Gaomiaozi Bentonite[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(4): 506-516.
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Carbon steel | C | Si | Mn | Al | Cr | Ni | Cu | Nb | V | Ti | Fe |
---|---|---|---|---|---|---|---|---|---|---|---|
X65 | 0.065 | 0.14 | 1.58 | 0.042 | 0.22 | 0.01 | 0.02 | 0.063 | 0.05 | 0.015 | Bal. |
Table 1 Chemical composition of X65 low carbon steel (wt%)
Carbon steel | C | Si | Mn | Al | Cr | Ni | Cu | Nb | V | Ti | Fe |
---|---|---|---|---|---|---|---|---|---|---|---|
X65 | 0.065 | 0.14 | 1.58 | 0.042 | 0.22 | 0.01 | 0.02 | 0.063 | 0.05 | 0.015 | Bal. |
Bentonite | SiO2 | Al2O3 | MgO | Na2O | Fe2O3 | K2O | CaO | TiO2 | Cr2O3 | P2O5 |
---|---|---|---|---|---|---|---|---|---|---|
Contents | 71.42 | 17.14 | 3.12 | 2.45 | 2.46 | 1.87 | 1.21 | 0.23 | 0.04 | 0.06 |
Table 2 Chemical composition of Gaomiaozi bentonite (wt%)
Bentonite | SiO2 | Al2O3 | MgO | Na2O | Fe2O3 | K2O | CaO | TiO2 | Cr2O3 | P2O5 |
---|---|---|---|---|---|---|---|---|---|---|
Contents | 71.42 | 17.14 | 3.12 | 2.45 | 2.46 | 1.87 | 1.21 | 0.23 | 0.04 | 0.06 |
Cations | Na+ | NH4+ | Ca2+ | K+ | Mg2+ | Sr2+ | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Contents | 1036.01 | 0.12 | 183.13 | 15.95 | 50.40 | 0.72 | ||||||
Anions | SO42- | Cl- | HCO3- | NO3- | F- | SiO32- | ||||||
Contents | 941.17 | 1193.26 | 150.92 | 72.61 | 2.27 | 13.82 |
Table 3 Chemical composition of Beishan groundwater (wt%)
Cations | Na+ | NH4+ | Ca2+ | K+ | Mg2+ | Sr2+ | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Contents | 1036.01 | 0.12 | 183.13 | 15.95 | 50.40 | 0.72 | ||||||
Anions | SO42- | Cl- | HCO3- | NO3- | F- | SiO32- | ||||||
Contents | 941.17 | 1193.26 | 150.92 | 72.61 | 2.27 | 13.82 |
Gamma irradiation dose rates | Weight loss (g) | Surface areas (cm2) | Corrosion rates (μm/year) | Average rates (μm/year) | Standard deviations (μm/year) | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Δm 1 | Δm 2 | Δm 3 | S 1 | S 2 | S 3 | ν 1 | ν 2 | ν 3 | ν avg | σ | |
0 kGy/h | 0.0168 | 0.0173 | 0.0162 | 2.6531 | 2.7053 | 2.6836 | 35.91 | 36.26 | 34.23 | 35.47 | 1.38 |
2.98 kGy/h | 0.0229 | 0.0216 | 0.0218 | 2.7607 | 2.7705 | 2.7753 | 46.92 | 44.12 | 44.44 | 45.16 | 1.53 |
Table 4 Weight loss and corrosion rates of X65 low carbon steel
Gamma irradiation dose rates | Weight loss (g) | Surface areas (cm2) | Corrosion rates (μm/year) | Average rates (μm/year) | Standard deviations (μm/year) | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Δm 1 | Δm 2 | Δm 3 | S 1 | S 2 | S 3 | ν 1 | ν 2 | ν 3 | ν avg | σ | |
0 kGy/h | 0.0168 | 0.0173 | 0.0162 | 2.6531 | 2.7053 | 2.6836 | 35.91 | 36.26 | 34.23 | 35.47 | 1.38 |
2.98 kGy/h | 0.0229 | 0.0216 | 0.0218 | 2.7607 | 2.7705 | 2.7753 | 46.92 | 44.12 | 44.44 | 45.16 | 1.53 |
Fig. 3 Surface morphologies of corrosion scale formed on X65 low carbon steel: a macro-morphology, b lamellar slices, c blocky particles, d amorphous swellings
Species | Fe | O | Si | Ca | Mg | Al | Na | Mn |
---|---|---|---|---|---|---|---|---|
Lamellar slices | 39.59 | 56.36 | 0.98 | 0.39 | 0.56 | 0.49 | 0.51 | 1.14 |
Blocky particles | 56.04 | 41.23 | 0.94 | 0.25 | 0.22 | 0.29 | 0.25 | 0.78 |
Amorphous swellings | 36.08 | 55.16 | 2.12 | 0.62 | 1.39 | 2.50 | 0.35 | 1.82 |
Table 5 Chemical composition of the corrosion scales with different morphology (at.%)
Species | Fe | O | Si | Ca | Mg | Al | Na | Mn |
---|---|---|---|---|---|---|---|---|
Lamellar slices | 39.59 | 56.36 | 0.98 | 0.39 | 0.56 | 0.49 | 0.51 | 1.14 |
Blocky particles | 56.04 | 41.23 | 0.94 | 0.25 | 0.22 | 0.29 | 0.25 | 0.78 |
Amorphous swellings | 36.08 | 55.16 | 2.12 | 0.62 | 1.39 | 2.50 | 0.35 | 1.82 |
Fig. 4 a Cross-sectional morphologies of the corrosion scale formed on X65 low carbon steel, b EPMA elemental distribution maps of the area marked by the dashed line rectangle in a
Fig. 5 a Bright-field image of cross section at corrosion front of X65 low carbon steel, b EDS line scan profiles alone the dashed line in a, c SAED for matrix, inner part scales, and outer part scale
Fig. 7 a-c μ-XRD spectra on the cross section of the corrosion scales formed on X65, d schematic diagram of the phase distribution on the cross section
Species | ΔfH m θ (298.15) (J/mol) | ΔfG m θ (298.15) (J/mol) | ΔfS m θ (298.15) (J/K mol-1) | ΔC p,m θ (298.15) (J/K mol-1) | ΔfG m,Cal θ (363.15) (J/mol) | ΔfG m,HSC θ (363.15) (J/mol) | Error (J/mol) | References |
---|---|---|---|---|---|---|---|---|
H2 (g) | 0 | 0 | 0 | 28.84 | 0 | 0 | 0 | [ |
O2 (g) | 0 | 0 | 0 | 29.38 | 0 | 0 | 0 | [ |
Fe (S) | 0 | 0 | 0 | 24.98 | 0 | 0 | 0 | [ |
H+ | 0 | 0 | 0 | 0 | 0 | 0 | 0 | [ |
Fe2+ | - 92,204.28 | - 91,451.59 | - 2.52 | - 33.03 | - 91,068.81 | - 91,218 | 149.19 | [ |
Fe3+ | - 49,551.96 | - 17,228.19 | - 108.41 | - 77.78 | - 9666.36 | - 9779 | 112.64 | [ |
HCO3- | - 689,537.48 | - 586,603.21 | - 345.24 | - 35.38 | - 563,928.21 | - 563,670 | - 258.21 | [ |
HFeO2- | - 525,627.12 | - 398,924.64 | - 424.96 | 92 | - 371,911.11 | - 371,240 | - 671.11 | [ |
H2O | - 285,830 | - 237,141 | - 163.30 | 75.29 | - 227,024.67 | - 226,736 | - 288.67 | [ |
Fe2O3 (S) | - 824,248 | - 742,294 | - 274.88 | 103.87 | - 725,114.71 | - 723,264 | - 1850.71 | [ |
Fe3O4 (S) | - 1,118,383 | - 1,015,227 | - 345.99 | 150.73 | - 993,735.68 | - 990,012 | - 3723.68 | [ |
FeCO3 (S) | - 740,568 | - 666,670 | - 247.86 | 82.08 | - 651,102.80 | - 650,595 | - 507.80 | [ |
Fe(OH)2(S) | - 568,999 | - 486,975 | - 275.11 | 97.04 | - 469,735.24 | - 474,155 | 4419.76 | [ |
FeOOH (S) | - 560,000 | - 489,229 | - 237.37 | 74.48 | - 474,293.20 | - 473,849 | - 444.20 | [ |
Table 6 Thermochemical data of the used species
Species | ΔfH m θ (298.15) (J/mol) | ΔfG m θ (298.15) (J/mol) | ΔfS m θ (298.15) (J/K mol-1) | ΔC p,m θ (298.15) (J/K mol-1) | ΔfG m,Cal θ (363.15) (J/mol) | ΔfG m,HSC θ (363.15) (J/mol) | Error (J/mol) | References |
---|---|---|---|---|---|---|---|---|
H2 (g) | 0 | 0 | 0 | 28.84 | 0 | 0 | 0 | [ |
O2 (g) | 0 | 0 | 0 | 29.38 | 0 | 0 | 0 | [ |
Fe (S) | 0 | 0 | 0 | 24.98 | 0 | 0 | 0 | [ |
H+ | 0 | 0 | 0 | 0 | 0 | 0 | 0 | [ |
Fe2+ | - 92,204.28 | - 91,451.59 | - 2.52 | - 33.03 | - 91,068.81 | - 91,218 | 149.19 | [ |
Fe3+ | - 49,551.96 | - 17,228.19 | - 108.41 | - 77.78 | - 9666.36 | - 9779 | 112.64 | [ |
HCO3- | - 689,537.48 | - 586,603.21 | - 345.24 | - 35.38 | - 563,928.21 | - 563,670 | - 258.21 | [ |
HFeO2- | - 525,627.12 | - 398,924.64 | - 424.96 | 92 | - 371,911.11 | - 371,240 | - 671.11 | [ |
H2O | - 285,830 | - 237,141 | - 163.30 | 75.29 | - 227,024.67 | - 226,736 | - 288.67 | [ |
Fe2O3 (S) | - 824,248 | - 742,294 | - 274.88 | 103.87 | - 725,114.71 | - 723,264 | - 1850.71 | [ |
Fe3O4 (S) | - 1,118,383 | - 1,015,227 | - 345.99 | 150.73 | - 993,735.68 | - 990,012 | - 3723.68 | [ |
FeCO3 (S) | - 740,568 | - 666,670 | - 247.86 | 82.08 | - 651,102.80 | - 650,595 | - 507.80 | [ |
Fe(OH)2(S) | - 568,999 | - 486,975 | - 275.11 | 97.04 | - 469,735.24 | - 474,155 | 4419.76 | [ |
FeOOH (S) | - 560,000 | - 489,229 | - 237.37 | 74.48 | - 474,293.20 | - 473,849 | - 444.20 | [ |
Number | Chemical reactions [ | Equilibrium equations |
---|---|---|
a | 2H+?+?2e-?=?H2 | Ea?=?-0.0721pH |
b | O2?+?4H+?+?4e-?=?2H2O | Eb?=?1.1765 - 0.0721pH |
A | Fe2+?+?2e-?=?Fe | EA?=?-0.4719?+?0.0360lg[Fe2+] |
B | Fe3+?+?e-?=?Fe2+ | EB?=?0.8437?+?0.0721{lg[Fe3+]?-?lg[Fe2+]} |
C | FeCO3?+?H+?=?Fe2+?+?HCO3- | lg[Fe2+]?+?lg[HCO3-]?=?0.5601?-?pH |
D | Fe2O3?+?6H+?=?2Fe3+?+?3H2O | lg[Fe3+]?=?-1.7770 - 3pH |
E | Fe2O3?+?6H+?+?2e-?=?2Fe2+?+?3H2O | EE?=?0.7156?-?0.2163pH - 0.0721lg[Fe2+] |
F | Fe2O3?+?2HCO3-?+?4H+?+?2e-?=?2FeCO3?+?3H2O | EF?=?0.6753?-?0.1442pH?+?0.0721lg[HCO3-] |
G | 3Fe2O3?+?2H+?+?2e-?=?2Fe3O4?+?H2O | EG?=?0.2029?-?0.0721pH |
H | Fe3O4?+?3HCO3-?+?5H+?+?2e-?=?3FeCO3?+?4H2O | EH?=?0.9115?-?0.1803pH?+?0.1082lg[HCO3-] |
I | FeCO3?+?H+?+?2e-?=?Fe?+?HCO3- | EI?=?-0.4518?-?0.0360pH - 0.0360lg[HCO3-] |
J | Fe3O4?+?8H+?+?8e-?=?3Fe?+?4H2O | EJ?=?-0.1109?-?0.0721pH |
Table 7 Chemical reactions and the corresponding equilibrium equations for the boundaries between the used species
Number | Chemical reactions [ | Equilibrium equations |
---|---|---|
a | 2H+?+?2e-?=?H2 | Ea?=?-0.0721pH |
b | O2?+?4H+?+?4e-?=?2H2O | Eb?=?1.1765 - 0.0721pH |
A | Fe2+?+?2e-?=?Fe | EA?=?-0.4719?+?0.0360lg[Fe2+] |
B | Fe3+?+?e-?=?Fe2+ | EB?=?0.8437?+?0.0721{lg[Fe3+]?-?lg[Fe2+]} |
C | FeCO3?+?H+?=?Fe2+?+?HCO3- | lg[Fe2+]?+?lg[HCO3-]?=?0.5601?-?pH |
D | Fe2O3?+?6H+?=?2Fe3+?+?3H2O | lg[Fe3+]?=?-1.7770 - 3pH |
E | Fe2O3?+?6H+?+?2e-?=?2Fe2+?+?3H2O | EE?=?0.7156?-?0.2163pH - 0.0721lg[Fe2+] |
F | Fe2O3?+?2HCO3-?+?4H+?+?2e-?=?2FeCO3?+?3H2O | EF?=?0.6753?-?0.1442pH?+?0.0721lg[HCO3-] |
G | 3Fe2O3?+?2H+?+?2e-?=?2Fe3O4?+?H2O | EG?=?0.2029?-?0.0721pH |
H | Fe3O4?+?3HCO3-?+?5H+?+?2e-?=?3FeCO3?+?4H2O | EH?=?0.9115?-?0.1803pH?+?0.1082lg[HCO3-] |
I | FeCO3?+?H+?+?2e-?=?Fe?+?HCO3- | EI?=?-0.4518?-?0.0360pH - 0.0360lg[HCO3-] |
J | Fe3O4?+?8H+?+?8e-?=?3Fe?+?4H2O | EJ?=?-0.1109?-?0.0721pH |
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