J. Mater. Sci. Technol. ›› 2017, Vol. 33 ›› Issue (5): 461-468.DOI: 10.1016/j.jmst.2017.01.021
Special Issue: 2017腐蚀与防护专辑
• Orginal Article • Previous Articles Next Articles
Mashtalyar D.V.ab*(), Gnedenkov S.V.a, Sinebryukhov S.L.a, Imshinetskiy I.M.a, Puz’ A.V.a
Received:
2016-09-21
Revised:
2016-10-19
Accepted:
2016-11-07
Online:
2017-05-20
Published:
2017-05-17
Contact:
Mashtalyar D.V.
About author:
These authors contributed equally to this work.
Mashtalyar D.V., Gnedenkov S.V., Sinebryukhov S.L., Imshinetskiy I.M., Puz’ A.V.. Plasma electrolytic oxidation of the magnesium alloy MA8 in electrolytes containing TiN nanoparticles[J]. J. Mater. Sci. Technol., 2017, 33(5): 461-468.
Fig. 1. Optical images of Mg alloy MA8 samples with PEO coatings formed in silicate-fluoride electrolyte without (a) and with TiN nanoparticle concentrations of 1 g l-1 (b), 2 g l-1 (c), 3 g l-1 (d) and 4 g l-1 (e).
Fig. 2. SEM images of surfaces (a, c, e, g, i) and cross-sections (b, d, f, h, j) of coatings obtained in silicate-fluoride electrolyte without (a, b) and with TiN nanoparticle concentration of 1 g l-1 (c, d), 2 g l-1 (e, f), 3 g l-1 (g, h) and 4 g l-1 (i, j) (The arrows show the particle agglomerates on the coating surface).
Fig. 3. EDS analysis of coating surface. (The upper line (white) shows the distribution of titanium throughout the line scan (red); data are presented for coating formed in electrolyte with 4 g l-1 of TiN particles.).
Concentration (g l-1) | Porosity (%) | Ra (μm) | Thickness (μm) | Average pore size (cross-section image) (μm) | |
---|---|---|---|---|---|
Surface | Cross-section | ||||
0 | 5.0 ± 0.4 | 16.8 ± 2.0 | 1.21 ± 0.11 | 20 ± 2 | 1.5 |
1 | 4.7 ± 0.4 | 14.0 ± 1.7 | 1.56 ± 0.16 | 19 ± 4 | 1.6 |
2 | 4.5 ± 0.4 | 13.5 ± 1.9 | 1.83 ± 0.14 | 21 ± 3 | 1.3 |
3 | 4.1 ± 0.4 | 12.2 ± 1.8 | 2.00 ± 0.20 | 20 ± 3 | 1.1 |
4 | 3.9 ± 0.3 | 11.9 ± 1.6 | 2.13 ± 0.19 | 21 ± 3 | 1.1 |
Table 1 Porosity and roughness of PEO coatings in silicate-fluroide electrolytes with different concentrations of TiN nanoparticles.
Concentration (g l-1) | Porosity (%) | Ra (μm) | Thickness (μm) | Average pore size (cross-section image) (μm) | |
---|---|---|---|---|---|
Surface | Cross-section | ||||
0 | 5.0 ± 0.4 | 16.8 ± 2.0 | 1.21 ± 0.11 | 20 ± 2 | 1.5 |
1 | 4.7 ± 0.4 | 14.0 ± 1.7 | 1.56 ± 0.16 | 19 ± 4 | 1.6 |
2 | 4.5 ± 0.4 | 13.5 ± 1.9 | 1.83 ± 0.14 | 21 ± 3 | 1.3 |
3 | 4.1 ± 0.4 | 12.2 ± 1.8 | 2.00 ± 0.20 | 20 ± 3 | 1.1 |
4 | 3.9 ± 0.3 | 11.9 ± 1.6 | 2.13 ± 0.19 | 21 ± 3 | 1.1 |
Fig. 4. XRD spectra of TiN powder and PEO coatings obtained in silicate-fluoride electrolyte without and with different concentrations of TiN nanoparticles.
Concentration (g l-1) | Element | ||||||
---|---|---|---|---|---|---|---|
Mg | O | Si | Ti | Na | Mn | N | |
0 | 39.4 | 38.2 | 18.3 | - | 1.2 | 2.9 | - |
1 | 41.9 | 38.1 | 15.1 | 1.0 | 1.9 | 1.7 | 0.3 |
2 | 42.5 | 37.5 | 14.5 | 1.1 | 2.4 | 1.7 | 0.3 |
3 | 40.1 | 38.0 | 15.3 | 1.8 | 2.6 | 1.7 | 0.5 |
4 | 38.6 | 37.8 | 16.1 | 2.2 | 3.1 | 1.6 | 0.6 |
Table 2 Element compositions (wt%) of PEO coatings in silicate-fluroide electrolytes with different concentrations of TiN nanoparticles.
Concentration (g l-1) | Element | ||||||
---|---|---|---|---|---|---|---|
Mg | O | Si | Ti | Na | Mn | N | |
0 | 39.4 | 38.2 | 18.3 | - | 1.2 | 2.9 | - |
1 | 41.9 | 38.1 | 15.1 | 1.0 | 1.9 | 1.7 | 0.3 |
2 | 42.5 | 37.5 | 14.5 | 1.1 | 2.4 | 1.7 | 0.3 |
3 | 40.1 | 38.0 | 15.3 | 1.8 | 2.6 | 1.7 | 0.5 |
4 | 38.6 | 37.8 | 16.1 | 2.2 | 3.1 | 1.6 | 0.6 |
Fig. 5. Cross-sectional SEM image of PEO coating in silicate-fluoride electrolyte with 4 g l-1 TiN nanoparticles and EDS elemental map for Mg (b), Si (c), O (d), Тi (e).
Fig. 6. Polarization curves of PEO coating on Mg alloy MA8 in 3% NaCl formed in silicate-fluoride electrolyte without and with different concentrations of TiN nanoparticles.
Concentration (g l-1) | βa (mV dec-1) | βc (mV dec-1) | Rp (Ω cm2) | IС (A cm-2) | EС (V vs. SCE) |
---|---|---|---|---|---|
0 | 302 ± 23 | 549 ± 25 | (7.1 ± 0.5) × 105 | (1.2 ± 0.1) × 10-7 | -1.37 ± 0.03 |
1 | 114 ± 15 | 170 ± 9 | (2.3 ± 0.3) × 105 | (1.4 ± 0.1) × 10-7 | -1.44 ± 0.04 |
2 | 162 ± 17 | 157 ± 7 | (2.1 ± 0.3) × 105 | (1.6 ± 0.1) × 10-7 | -1.45 ± 0.03 |
3 | 118 ± 11 | 186 ± 8 | (1.7 ± 0.2) × 105 | (1.8 ± 0.2) × 10-7 | -1.47 ± 0.02 |
4 | 61 ± 8 | 163 ± 6 | (6.0 ± 0.4) × 104 | (7.9 ± 0.6) × 10-7 | -1.50 ± 0.04 |
Table 3 Corrosion characteristics of PEO coating on Mg alloy MA8 in silicate-fluroide electrolytes with different concentrations of TiN nanoparticles.
Concentration (g l-1) | βa (mV dec-1) | βc (mV dec-1) | Rp (Ω cm2) | IС (A cm-2) | EС (V vs. SCE) |
---|---|---|---|---|---|
0 | 302 ± 23 | 549 ± 25 | (7.1 ± 0.5) × 105 | (1.2 ± 0.1) × 10-7 | -1.37 ± 0.03 |
1 | 114 ± 15 | 170 ± 9 | (2.3 ± 0.3) × 105 | (1.4 ± 0.1) × 10-7 | -1.44 ± 0.04 |
2 | 162 ± 17 | 157 ± 7 | (2.1 ± 0.3) × 105 | (1.6 ± 0.1) × 10-7 | -1.45 ± 0.03 |
3 | 118 ± 11 | 186 ± 8 | (1.7 ± 0.2) × 105 | (1.8 ± 0.2) × 10-7 | -1.47 ± 0.02 |
4 | 61 ± 8 | 163 ± 6 | (6.0 ± 0.4) × 104 | (7.9 ± 0.6) × 10-7 | -1.50 ± 0.04 |
Fig. 7. Bode diagrams of PEO coatings on Mg alloy MA8 in silicate-fluoride electrolyte without and with different concentrations of TiN nanoparticles. (Symbols are the experimental data, while the solid lines are fitting curves).
Fig. 8. Equivalent electric circuit used for simulation of charge transfer process at Mg alloy with coating/electrolyte interface, according to the experimental impedance spectra data.
Concentration (g l-1) | |Z|f → 0 Hz (Ω cm2) | R1 | CPE1 ----------- | R2 | CPE2 ------------ | ||
---|---|---|---|---|---|---|---|
Q1 | n | Q2 | n | ||||
0 | 1.4 × 105 | 1.91 × 104 | 4.09 × 10-7 | 0.72 | 1.20 × 105 | 9.98 × 10-7 | 0.77 |
1 | 1.3 × 105 | 7.16 × 103 | 1.60 × 10-7 | 0.78 | 1.19 × 105 | 3.80 × 10-6 | 0.78 |
2 | 8.8 × 104 | 4.81 × 103 | 1.65 × 10-7 | 0.78 | 6.73 × 104 | 4.72 × 10-6 | 0.80 |
3 | 5.2 × 104 | 3.42 × 103 | 2.13 × 10-7 | 0.78 | 4.96 × 104 | 5.60 × 10-6 | 0.76 |
4 | 2.1 × 104 | 1.56 × 103 | 3.82 × 10-7 | 0.74 | 2.13 × 104 | 1.05 × 10-5 | 0.79 |
Table 4 Calculated parameters of equivalent electric circuit elements (R, Ω cm2; Q, Ω-1 cm-2 сn. R1 and R2 are the resistances of porous and nonporous layers of coating, Q1 and Q2 are pre-exponential factors, and n is the exponential coefficient of CPEs) fitting experimental impedance spectra of PEO coating on Mg alloy MA8 in silicate-fluroide electrolytes with different concentrations of TiN nanoparticles.
Concentration (g l-1) | |Z|f → 0 Hz (Ω cm2) | R1 | CPE1 ----------- | R2 | CPE2 ------------ | ||
---|---|---|---|---|---|---|---|
Q1 | n | Q2 | n | ||||
0 | 1.4 × 105 | 1.91 × 104 | 4.09 × 10-7 | 0.72 | 1.20 × 105 | 9.98 × 10-7 | 0.77 |
1 | 1.3 × 105 | 7.16 × 103 | 1.60 × 10-7 | 0.78 | 1.19 × 105 | 3.80 × 10-6 | 0.78 |
2 | 8.8 × 104 | 4.81 × 103 | 1.65 × 10-7 | 0.78 | 6.73 × 104 | 4.72 × 10-6 | 0.80 |
3 | 5.2 × 104 | 3.42 × 103 | 2.13 × 10-7 | 0.78 | 4.96 × 104 | 5.60 × 10-6 | 0.76 |
4 | 2.1 × 104 | 1.56 × 103 | 3.82 × 10-7 | 0.74 | 2.13 × 104 | 1.05 × 10-5 | 0.79 |
Concentration (g l-1) | Hμ (GPa) | Young’s modulus (GPa) |
---|---|---|
0 | 2.1 ± 0.3 | 60 ± 5 |
1 | 2.2 ± 0.3 | 62 ± 7 |
2 | 4.5 ± 0.5 | 102 ± 12 |
3 | 4.2 ± 0.5 | 98 ± 10 |
4 | 3.7 ± 0.3 | 97 ± 10 |
Table 5 Microhardness and elasticity modulus of PEO coatings formed on magnesium alloy МА8 with different concentrations of TiN nanoparticles.
Concentration (g l-1) | Hμ (GPa) | Young’s modulus (GPa) |
---|---|---|
0 | 2.1 ± 0.3 | 60 ± 5 |
1 | 2.2 ± 0.3 | 62 ± 7 |
2 | 4.5 ± 0.5 | 102 ± 12 |
3 | 4.2 ± 0.5 | 98 ± 10 |
4 | 3.7 ± 0.3 | 97 ± 10 |
Fig. 9. External appearances of scratch for PEO coatings on Mg alloy MA8 in silicate-fluoride electrolyte without (a) and with TiN nanoparticle concentrations of 1 g l-1 (b), 2 g l-1 (c), 3 g l-1 (d) and 4 g l-1 (e).
Concentration (g l-1) | LС2 (N) | LС3 (N) |
---|---|---|
0 | 8.4 ± 0.9 | 11.0 ± 1.5 |
1 | 8.6 ± 0.8 | 15.6 ± 1.7 |
2 | 10.1 ± 1.1 | 19.1 ± 1.3 |
3 | 10.5 ± 0.9 | 20.4 ± 1.9 |
4 | 9.3 ± 1.0 | 17.9 ± 1.6 |
Table 6 Critical loads of PEO coatings determined by scratch testing.
Concentration (g l-1) | LС2 (N) | LС3 (N) |
---|---|---|
0 | 8.4 ± 0.9 | 11.0 ± 1.5 |
1 | 8.6 ± 0.8 | 15.6 ± 1.7 |
2 | 10.1 ± 1.1 | 19.1 ± 1.3 |
3 | 10.5 ± 0.9 | 20.4 ± 1.9 |
4 | 9.3 ± 1.0 | 17.9 ± 1.6 |
Fig. 10. Dependence of friction coefficient on number of cycles for PEO coating on Mg alloy MA8 in silicate-fluoride electrolyte without and with different concentrations of TiN nanoparticles.e
Concentration (g l-1) | Wear (mm3 N-1 m-1) | Number of cycles until coating abrasion |
---|---|---|
0 | (1.1 ± 0.1) × 10-5 | 273 ± 21 |
1 | (7.3 ± 0.6) × 10-6 | 319 ± 25 |
2 | (5.8 ± 0.5) × 10-6 | 464 ± 34 |
3 | (5.0 ± 0.4) × 10-6 | 605 ± 53 |
4 | (6.5 ± 0.5) × 10-6 | 417 ± 32 |
Table 7 Tribological properties of PEO coatings with different concentrations of TiN nanoparticles.
Concentration (g l-1) | Wear (mm3 N-1 m-1) | Number of cycles until coating abrasion |
---|---|---|
0 | (1.1 ± 0.1) × 10-5 | 273 ± 21 |
1 | (7.3 ± 0.6) × 10-6 | 319 ± 25 |
2 | (5.8 ± 0.5) × 10-6 | 464 ± 34 |
3 | (5.0 ± 0.4) × 10-6 | 605 ± 53 |
4 | (6.5 ± 0.5) × 10-6 | 417 ± 32 |
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