Electrochemical and Mechanical Properties of Hexagonal Titanium Dioxide Nanotubes Formed by Sonoelectrochemical Anodization
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Hexagonal TiO2 Nanotube Fabrication
2.3. Electrochemical Measurements
2.4. Mechanical Properties’ Measurements
3. Results and Discussion
3.1. Microscopic and Structural Characterization of Varying Morphology of Titanium Dioxide
3.2. Electrochemical Characterization of Compact and Hexagonal TiO2 Layer
3.3. Corrosion Analysis of hTNTs
3.4. Nanoindentation Tests
3.5. Influence of Diagonality of hTNTs on Electrochemical and Mechanical Properties
4. Conclusions
- An increase in the diagonal of the hTNTs resulted in a decrease in the open-circuit potential values, indicating deterioration in the corrosion properties.
- An electrochemical impedance spectroscopy analysis revealed that the hTNTs possessed a lower impedance modulus than compact TiO2, indicating better charge transfer kinetics.
- The hTNTs exhibited lower corrosion rates and higher corrosion potentials than the compact TiO2 layers.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Type of TiO2 Layer | Time [min] | Potential [V] | Ethylene Glycol Concentration [%] | Ammonium Fluoride Concentration [M] | Disodium Edetate Concentration [M] |
---|---|---|---|---|---|
Compact | 60 | 80 | 95 | - | 0.0030 |
Hexagonal | 60 | 10 | 95 | 0.818 | |
60 | 20 | 94 | |||
60 | 35 | 95 | |||
50 | 50 | 90 |
Morphology | EDS Analysis | ||||
---|---|---|---|---|---|
Sample | Diagonal [nm] | Height [nm] | Ti [% wt.] | O [% wt.] | F [% wt.] |
Compact TiO2 | - | 370 ± 58 | 66.88 ± 3.08 | 33.13 ± 3.08 | - |
30 nm hTNTs | 30 ± 5 | 3707 ± 97 | 57.73 ± 4.40 | 34.26 ± 4.04 | 8.02 ± 0.93 |
45 nm hTNTs | 46 ± 8 | 3790 ± 585 | 62.68 ± 2.63 | 28.58 ± 2.28 | 8.88 ± 0.39 |
80 nm hTNTs | 82 ± 9 | 4068 ± 104 | 60.77 ± 1.85 | 30.05 ± 1.58 | 9.18 ± 0.40 |
95 nm hTNTs | 93 ± 13 | 3564 ± 102 | 58.00 ± 3.22 | 31.45 ± 1.92 | 10.55 ± 1.38 |
Sample | |Z| [Ω] | ReZ [Ω] | −ImZ [Ω] | −Z Phase [°] | OCP [mV] |
---|---|---|---|---|---|
3.5% NaCl | |||||
Compact TiO2 | 198,293 ± 34,704 | 71,598 ± 8582 | 185,054 ± 32,366 | 69 ± 1 | −33 ± 3 |
30 nm hTNTs | 19,097 ± 2671 | 9050 ± 1511 | 16,805 ± 2301 | 62 ± 2 | −157 ± 25 |
45 nm hTNTs | 5259 ± 1958 | 3279 ± 1210 | 4109 ± 1546 | 51 ± 2 | −191 ± 17 |
80 nm hTNTs | 10,237 ± 1033 | 7990 ± 823 | 6389 ± 749 | 39 ± 2 | −206 ± 15 |
95 nm hTNTs | 12,212 ± 1512 | 9500 ± 1436 | 7660 ± 698 | 39 ± 2 | −213 ± 17 |
RINGER | |||||
Compact TiO2 | 193,779 ± 17,420 | 56,695 ± 4348 | 185,230 ± 17,792 | 73 ± 2 | 103 ± 10 |
30 nm hTNTs | 16,196 ± 1080 | 8018 ± 385 | 14,048 ± 1368 | 60 ± 3 | −138 ± 20 |
45 nm hTNTs | 8423 ± 1665 | 5549 ± 1078 | 6329 ± 1320 | 49 ± 2 | −149 ± 11 |
80 nm hTNTs | 10,960 ± 3065 | 7742 ± 2023 | 7743 ± 2362 | 45 ± 3 | −198 ± 13 |
95 nm hTNTs | 24,893 ± 7297 | 18,313 ± 5982 | 16,821 ± 4388 | 43 ± 3 | −210 ± 31 |
EC Parameter | 30 nm hTNTs | 45 nm hTNTs | 80 nm hTNTs | 95 nm hTNTs | Compact TiO2 | |||||
---|---|---|---|---|---|---|---|---|---|---|
Value | SD | Value | SD | Value | SD | Value | SD | Value | SD | |
3.5% NaCl | ||||||||||
Rs [Ω∙cm2] | 5.53 | 0.55 | 6.71 | 1.16 | 7.85 | 1.05 | 8.19 | 0.75 | 8.22 | 0.25 |
Y1 [S/cm2] | 8.90 × 10−5 | 1.04 × 10−5 | 2.98 × 10−4 | 1.07 × 10−4 | 1.94 × 10−4 | 2.58 × 10−5 | 1.64 × 10−4 | 1.02 × 10−5 | 7.57 × 10−6 | 1.08 × 10−6 |
N1 | 0.81 | 0.03 | 0.69 | 0.01 | 0.71 | 0.01 | 0.71 | 0.01 | 0.83 | 0.01 |
R1 [Ω∙cm2] | 5.60 | 0.59 | 6.86 | 1.23 | 8.06 | 1.12 | 8.65 | 0.91 | 7.10 | 0.25 |
Y2 [S/cm2] | 1.01 × 10−4 | 3.96 × 10−5 | 1.03 × 10−4 | 4.45 × 10−5 | 3.03 × 10−5 | 3.59 × 10−6 | 3.26 × 10−5 | 8.06 × 10−6 | 2.26 × 10−6 | 3.54 × 10−7 |
N2 | 0.87 | 0.02 | 0.83 | 0.05 | 0.96 | 0.02 | 0.97 | 0.02 | 0.84 | 0.01 |
R2 [Ω∙cm2] | 3729 | 1965 | 1046 | 507 | 3528 | 157 | 4147 | 724 | 67 | 9 |
χ2 | 0.04 | 0.01 | 0.04 | 0.01 | 0.24 | 0.06 | 0.38 | 0.07 | 0.05 | 0.01 |
τ1 = R1∙Y1 | 4.99 × 10−4 | 2.05 × 10−3 | 1.56 × 10−3 | 1.42 × 10−3 | 5.38 × 10−5 | |||||
τ2 = R2∙Y2 | 3.78 × 10−1 | 1.07 × 10−1 | 1.07 × 10−1 | 1.35 × 10−1 | 1.50 × 10−4 | |||||
RINGER | ||||||||||
Value | SD | Value | SD | Value | SD | Value | SD | Value | SD | |
Rs [Ω∙cm2] | 28.61 | 0.67 | 29.60 | 0.70 | 31.90 | 1.23 | 31.20 | 0.01 | 31.39 | 2.12 |
Y1 [S/cm2] | 8.90 × 10−5 | 3.58 × 10−6 | 1.95 × 10−4 | 3.39 × 10−5 | 1.41 × 10−4 | 3.21 × 10−5 | 9.50 × 10−5 | 1.50 × 10−5 | 7.70 × 10−6 | 6.22 × 10−7 |
N1 | 0.74 | 0.01 | 0.67 | 0.02 | 0.63 | 0.05 | 0.66 | 0.04 | 0.85 | 0.01 |
R1 [Ω∙cm2] | 46.30 | 2.16 | 49.31 | 2.66 | 58.48 | 5.06 | 61.84 | 5.31 | 50.48 | 6.12 |
Y2 [S/cm2] | 1.38 × 10−4 | 2.55 × 10−5 | 8.01 × 10−5 | 1.52 × 10−5 | 4.02 × 10−5 | 4.02 × 10−6 | 3.77 × 10−5 | 8.42 × 10−6 | 2.26 × 10−6 | 3.20 × 10−7 |
N2 | 0.87 | 0.04 | 0.85 | 0.04 | 1.06 | 0.02 | 1.08 | 0.02 | 0.85 | 0.01 |
R2 [Ω∙cm2] | 565 | 271 | 1718 | 522 | 2321 | 1035 | 4326 | 97 | 215 | 78 |
χ2 | 0.02 | 0.01 | 0.02 | 0.01 | 0.18 | 0.05 | 0.44 | 0.07 | 0.03 | 0.02 |
τ1 = R1∙Y1 | 4.12 × 10−3 | 9.64 × 10−3 | 8.22 × 10−3 | 5.88 × 10−3 | 3.89 × 10−4 | |||||
τ2 = R2∙Y2 | 7.81 × 10−2 | 1.38 × 10−1 | 9.34 × 10−2 | 1.63 × 10−1 | 4.86 × 10−4 |
Sample | icorr [A/cm2] | Ecorr [mV] | Rp [Ω/cm2] | Corrosion Rate [mm/year] |
---|---|---|---|---|
3.5% NaCl | ||||
Compact TiO2 | 3.40 × 10−8 ± 5.29 × 10−9 | −244 ± 2 | 1,381,172 ± 143,814 | 0.0024 ± 0.0004 |
30 nm hTNTs | 4.01 × 10−7 ± 4.76 × 10−8 | −363 ± 8 | 69,447 ± 9927 | 0.027 ± 0.0033 |
45 nm hTNTs | 2.96 × 10−7 ± 9.49 × 10−8 | −411 ± 5 | 20,557 ± 5518 | 0.021 ± 0.0034 |
80 nm hTNTs | 2.63 × 10−7 ± 8.33 × 10−9 | −393 ± 5 | 54,904 ± 3068 | 0.017 ± 0.0006 |
95 nm hTNTs | 4.19 × 10−7 ± 4.08 × 10−8 | −386 ± 1 | 45,702 ± 3246 | 0.025 ± 0.0028 |
RINGER | ||||
Compact TiO2 | 1.90 × 10−8 ± 7.07 × 10−10 | −226 ± 5 | 1,107,176 ± 262,155 | 0.002 ± 0.00004 |
30 nm hTNTs | 1.22 × 10−7 ± 1.72 × 10−8 | −372 ± 2 | 133,634 ± 7437 | 0.008 ± 0.001 |
45 nm hTNTs | 5.32 × 10−7 ± 9.22 × 10−8 | −357 ± 7 | 55,642 ± 1805 | 0.038 ± 0.006 |
80 nm hTNTs | 2.76 × 10−7 ± 1.13 × 10−8 | −364 ± 2 | 86,066 ± 15,194 | 0.022 ± 0.0008 |
95 nm hTNTs | 3.41 × 10−7 ± 9.87 × 10−9 | −351 ± 10 | 82,370 ± 6434 | 0.023 ± 0.0007 |
Sample | Martens Hardness [N/mm2] | Vickers Hardness [N/mm2] | Young’s Modulus [GPa] | Plastic Deformation [%] |
---|---|---|---|---|
Compact TiO2 | 3152.45 ± 402.33 | 395.16 ± 54.00 | 151.39 ± 19.96 | 76.705 ± 2.518 |
30 nm hTNTs | 1328.48 ± 154.20 | 154.20 ± 32.42 | 99.48 ± 10.42 | 80.736 ± 1.372 |
45 nm hTNTs | 711.21 ± 63.26 | 80.44 ± 7.07 | 76.49 ± 8.07 | 85.087 ± 0.604 |
80 nm hTNTs | 272.93 ± 25.14 | 29.75 ± 2.74 | 54.74 ± 2.61 | 93.132 ± 1.067 |
95 nm hTNTs | 379.71 ± 26.18 | 41.85 ± 2.99 | 65.19 ± 3.68 | 90.698 ± 0.812 |
TNT (Diameter/Diagonal × Height) [nm] | Young’s Modulus [GPa] | Reference |
---|---|---|
20–150 × 210–1920 | 36–43 | [55] |
45–50 × 234–625 | 4.6–32.8 | [56] |
198 × 8500 | 5.1 | [57] |
43–58 × 234–650 | 36–43 | [58] |
31–128 × 240–3500 | ~10 | [59] |
75–110 × 7000–10,000 | 23−44 | [60] |
80 × 10,000 | 57 | [61] |
15–100 × 200 | 8.7–19.2 | [62] |
100 × 4000 | ~35 | [63] |
30–95 × 3500–4000 | 54–99 | [this manuscript] |
Diagonal of hTNTs | OCP [mV] | |Z| [Ω] | Corrosion Rate [mm/year] | Martens Hardness [N/mm2] | Vickers Hardness [N/mm2] | Young’s Modulus [GPa] | Plastic Deformation [%] |
---|---|---|---|---|---|---|---|
3.5% NaCl | |||||||
30 ± 5 | −157 ± 25 | 19,097 ± 2671 | 0.027 ± 0.0033 | 1328.48 ± 154.20 | 154.20 ± 32.42 | 99.48 ± 10.42 | 80.736 ± 1.372 |
46 ± 8 | −191 ± 17 | 5259 ± 1958 | 0.021 ± 0.0034 | 711.21 ± 63.26 | 80.44 ± 7.07 | 76.49 ± 8.07 | 85.087 ± 0.604 |
82 ± 9 | −206 ± 15 | 10,237 ± 1033 | 0.017 ± 0.0006 | 272.93 ± 25.14 | 29.75 ± 2.74 | 54.74 ± 2.61 | 93.132 ± 1.067 |
93 ± 13 | −213 ± 17 | 12,212 ± 1512 | 0.025 ± 0.0028 | 379.71 ± 26.18 | 41.85 ± 2.99 | 65.19 ± 3.68 | 90.698 ± 0.812 |
RINGER | |||||||
30 ± 5 | −138 ± 20 | 16,196 ± 1080 | 0.008 ± 0.001 | 1328.48 ± 154.20 | 154.20 ± 32.42 | 99.48 ± 10.42 | 80.736 ± 1.372 |
46 ± 8 | −149 ± 11 | 8423 ± 1665 | 0.038 ± 0.006 | 711.21 ± 63.26 | 80.44 ± 7.07 | 76.49 ± 8.07 | 85.087 ± 0.604 |
82 ± 9 | −198 ± 13 | 10,960 ± 3065 | 0.022 ± 0.0008 | 272.93 ± 25.14 | 29.75 ± 2.74 | 54.74 ± 2.61 | 93.132 ± 1.067 |
93 ± 13 | −210 ± 31 | 24,893 ± 7297 | 0.023 ± 0.0007 | 379.71 ± 26.18 | 41.85 ± 2.99 | 65.19 ± 3.68 | 90.698 ± 0.812 |
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Arkusz, K.; Jędrzejewska, A.; Siwak, P.; Jurczyk, M. Electrochemical and Mechanical Properties of Hexagonal Titanium Dioxide Nanotubes Formed by Sonoelectrochemical Anodization. Materials 2024, 17, 2138. https://doi.org/10.3390/ma17092138
Arkusz K, Jędrzejewska A, Siwak P, Jurczyk M. Electrochemical and Mechanical Properties of Hexagonal Titanium Dioxide Nanotubes Formed by Sonoelectrochemical Anodization. Materials. 2024; 17(9):2138. https://doi.org/10.3390/ma17092138
Chicago/Turabian StyleArkusz, Katarzyna, Aleksandra Jędrzejewska, Piotr Siwak, and Mieczysław Jurczyk. 2024. "Electrochemical and Mechanical Properties of Hexagonal Titanium Dioxide Nanotubes Formed by Sonoelectrochemical Anodization" Materials 17, no. 9: 2138. https://doi.org/10.3390/ma17092138