Acta Metallurgica Sinica (English Letters) ›› 2020, Vol. 33 ›› Issue (10): 1331-1345.DOI: 10.1007/s40195-020-01081-5
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Wen-Ya Zhang1, Can-Ming Wang1(
), Jing-Xin Ji1, Xiao-Li Feng1, Hong-Zhi Cui1(), Qiang Song1, Chun-Zhi Zhang1
Received:2020-01-02
Revised:2020-02-23
Online:2020-10-10
Published:2020-10-20
Contact:
Can-Ming Wang,Hong-Zhi Cui
Wen-Ya Zhang, Can-Ming Wang, Jing-Xin Ji, Xiao-Li Feng, Hong-Zhi Cui, Qiang Song, Chun-Zhi Zhang. Synthetic Effect of Cr and Mo Elements on Microstructure and Properties of Laser Cladding NiCrxMoy Alloy Coatings[J]. Acta Metallurgica Sinica (English Letters), 2020, 33(10): 1331-1345.
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| Alloy coatings | Composition (at.%) | ||
|---|---|---|---|
| Ni | Cr | Mo | |
| NiCr | 50 | 50 | - |
| NiCrMo0.1 | 47.62 | 47.62 | 4.76 |
| NiCrMo0.3 | 43.48 | 43.48 | 13.04 |
| NiCr1.5 | 40 | 60 | - |
| NiCr1.5Mo0.1 | 38.46 | 57.69 | 3.85 |
| NiCr1.5Mo0.3 | 35.71 | 53.57 | 10.71 |
Table 1 Compositions of NiCrxMoy alloy coating powders
| Alloy coatings | Composition (at.%) | ||
|---|---|---|---|
| Ni | Cr | Mo | |
| NiCr | 50 | 50 | - |
| NiCrMo0.1 | 47.62 | 47.62 | 4.76 |
| NiCrMo0.3 | 43.48 | 43.48 | 13.04 |
| NiCr1.5 | 40 | 60 | - |
| NiCr1.5Mo0.1 | 38.46 | 57.69 | 3.85 |
| NiCr1.5Mo0.3 | 35.71 | 53.57 | 10.71 |
Fig. 1 Surface morphology of a Ni powder, b Cr powder, c Mo powder
Fig. 2 Schematic diagram of the laser cladding system
Fig. 3 XRD patterns of NiCrxMoy alloy coatings
Fig. 4 SEM micrographs of the NiCrxMoy alloy coatings: a, a1 secondary electron (SE) image of the NiCr coating, b SE image of the NiCrMo0.1 coating, b1 backscattered electron (BSE) image of the NiCrMo0.1 coating at high magnification, c SE image of the NiCrMo0.3 coating, c1 BSE image of the NiCrMo0.3 coating at high magnification, d, d1 SE images of the NiCr1.5 coating, e, e1 SE images of the NiCr1.5Mo0.1 coating, f, f1, f2 SE images of the NiCr1.5Mo0.3 coating
| Alloy coatings | Area | Ni | Fe | Cr | Mo |
|---|---|---|---|---|---|
| NiCr | DR | 38.02 | 25.31 | 36.67 | - |
| NiCrMo0.1 | DR | 33.26 | 32.57 | 30.88 | 3.29 |
| IDM | 31.92 | 29.94 | 33.66 | 4.48 | |
| B | 23.43 | 25.81 | 41.15 | 9.61 | |
| NiCrMo0.3 | DR | 27.12 | 40.83 | 24.76 | 7.29 |
| IDM | 27.62 | 39.78 | 25.07 | 7.52 | |
| B | 19.69 | 35.01 | 29.80 | 15.49 | |
| NiCr1.5 | DR | 38.39 | 17.71 | 43.90 | - |
| ID | 26.32 | 16.93 | 56.75 | - | |
| NiCr1.5Mo0.1 | DR | 34.35 | 25.08 | 37.56 | 3.01 |
| ID | 19.71 | 23.02 | 52.01 | 5.27 | |
| NiCr1.5Mo0.3 | DR | 23.32 | 23.51 | 41.80 | 11.37 |
| ID | 22.43 | 22.78 | 44.21 | 10.58 |
Table 2 Chemical composition (at.%) of different areas of the NiCrxMoy alloy coatings
| Alloy coatings | Area | Ni | Fe | Cr | Mo |
|---|---|---|---|---|---|
| NiCr | DR | 38.02 | 25.31 | 36.67 | - |
| NiCrMo0.1 | DR | 33.26 | 32.57 | 30.88 | 3.29 |
| IDM | 31.92 | 29.94 | 33.66 | 4.48 | |
| B | 23.43 | 25.81 | 41.15 | 9.61 | |
| NiCrMo0.3 | DR | 27.12 | 40.83 | 24.76 | 7.29 |
| IDM | 27.62 | 39.78 | 25.07 | 7.52 | |
| B | 19.69 | 35.01 | 29.80 | 15.49 | |
| NiCr1.5 | DR | 38.39 | 17.71 | 43.90 | - |
| ID | 26.32 | 16.93 | 56.75 | - | |
| NiCr1.5Mo0.1 | DR | 34.35 | 25.08 | 37.56 | 3.01 |
| ID | 19.71 | 23.02 | 52.01 | 5.27 | |
| NiCr1.5Mo0.3 | DR | 23.32 | 23.51 | 41.80 | 11.37 |
| ID | 22.43 | 22.78 | 44.21 | 10.58 |
Fig. 5 EDS maps of a NiCrMo0.1, b NiCrMo0.3, c NiCr1.5Mo0.1 coatings
| Area | Ni | Fe | Cr | Mo |
|---|---|---|---|---|
| A | 40.19 | 14.35 | 42.47 | 2.97 |
| B | 30.81 | 14.63 | 51.91 | 2.63 |
| C | 23.04 | 14.14 | 59.66 | 3.14 |
| D | 20.00 | 13.16 | 61.18 | 5.64 |
| E | 47.90 | 18.46 | 32.61 | 1.01 |
Table 3 Composition (at.%) in different regions marked in Fig. 6
| Area | Ni | Fe | Cr | Mo |
|---|---|---|---|---|
| A | 40.19 | 14.35 | 42.47 | 2.97 |
| B | 30.81 | 14.63 | 51.91 | 2.63 |
| C | 23.04 | 14.14 | 59.66 | 3.14 |
| D | 20.00 | 13.16 | 61.18 | 5.64 |
| E | 47.90 | 18.46 | 32.61 | 1.01 |
Fig. 6 TEM micrographs of NiCr1.5Mo0.1 alloy coating: a, b, c bright-field (BF) images of the NiCr1.5Mo0.1coating, d HRTEM image of region C, e HRTEM image of region D, f HRTEM image of region E, g SAED-pattern of region A in a, h corresponding fast Fourier transformation patterns of region in d, i corresponding fast Fourier transformation patterns of region in e, j corresponding fast Fourier transformation patterns of region in f
Fig. 7 a Solidification phase transformation process, b a schematic diagram of the NiCr1.5Mo0.1 coating
Fig. 8 Potentiodynamic polarization curves of a NiCrMoy alloy coatings, b NiCr1.5Moy alloy coatings, c NiCrxMoy (x = 1, 1.5; y = 0, 0.1) alloy coatings
| Alloy coatings | Ecorr (mV) | icorr (μA/cm2) | Etr (mV) | Epp (mV) | Eb (mV) | ?E |
|---|---|---|---|---|---|---|
| NiCr | - 180.2 | 9.91 × 10-2 | 917.5 | 339.8 | 708.7 | 368.9 |
| NiCrMo0.1 | - 167.4 | 4.88 × 10-2 | 932.0 | - 53.4 | 907.8 | 961.2 |
| NiCrMo0.3 | - 321.7 | 1.79 × 10-1 | 975.7 | - 184.5 | 970.9 | 1155.4 |
| NiCr1.5 | - 201.1 | 2.92 × 10-2 | 847.5 | 72.7 | 847.5 | 774.8 |
| NiCr1.5Mo0.1 | - 185.7 | 4.52 × 10-3 | 941.7 | 101.9 | 912.6 | 810.7 |
| NiCr1.5Mo0.3 | - 415.9 | 1.71 | 1002.0 | - 241.5 | 978.2 | 1219.7 |
Table 4 Electrochemical parameters of the NiCrxMoy alloy coatings in 3.5 wt% NaCl solution
| Alloy coatings | Ecorr (mV) | icorr (μA/cm2) | Etr (mV) | Epp (mV) | Eb (mV) | ?E |
|---|---|---|---|---|---|---|
| NiCr | - 180.2 | 9.91 × 10-2 | 917.5 | 339.8 | 708.7 | 368.9 |
| NiCrMo0.1 | - 167.4 | 4.88 × 10-2 | 932.0 | - 53.4 | 907.8 | 961.2 |
| NiCrMo0.3 | - 321.7 | 1.79 × 10-1 | 975.7 | - 184.5 | 970.9 | 1155.4 |
| NiCr1.5 | - 201.1 | 2.92 × 10-2 | 847.5 | 72.7 | 847.5 | 774.8 |
| NiCr1.5Mo0.1 | - 185.7 | 4.52 × 10-3 | 941.7 | 101.9 | 912.6 | 810.7 |
| NiCr1.5Mo0.3 | - 415.9 | 1.71 | 1002.0 | - 241.5 | 978.2 | 1219.7 |
| Alloy | Ecorr (mV) | icorr (μA/cm2) | Epp (mV) | References |
|---|---|---|---|---|
| NiCr1.5Mo0.1 | - 185.7 | 4.52 × 10-3 | 101.9 | This work |
| NiCr | - 180.2 | 9.91 × 10-2 | 339.8 | This work |
| Co1.5CrFeNi1.5Ti0.5 | - 443 | 5.7 × 10-1 | - 219 | [ |
| Co1.5CrFeNi1.5Ti0.5Mo0.1 | - 381 | 1.3 × 10-1 | - 215 | [ |
| Co1.5CrFeNi1.5Ti0.5Mo0.5 | - 493 | 2.0 × 10-1 | - 219 | [ |
| Co1.5CrFeNi1.5Ti0.5Mo0.8 | - 551 | 4.1 × 10-1 | - 189 | [ |
| 45# steel | - 601 | 1.028 × 10-2 | - 343 | [ |
| AlCoCr0.5FeNi | - 458 | 7.622 × 10-3 | - 161 | [ |
| AlCoCr0.75FeNi | - 326 | 1.687 × 10-4 | - 276 | [ |
| AlCoCrFeNi | - 270 | 7.113 × 10-5 | - 208 | [ |
| AlCoCr1.5FeNi | - 163 | 2.455 × 10-5 | - 105 | [ |
| AlCoCr2FeNi | - 357 | 3.177 × 10-4 | - 86 | [ |
| 304 SS | - 272 | 1.35 × 10-1 | 132 | [ |
| CoCrFeNiMo0.1 | - 263 | 3.81 × 10-1 | - 638 | [ |
| CoCrFeNiMo0.2 | - 131 | 7.2 × 10-2 | - 661 | [ |
| CoCrFeNiMo0.3 | - 257 | 7.66 × 10-1 | - 656 | [ |
| CoCrFeNiMo0.4 | - 261 | 8.2 × 10-2 | - 576 | [ |
| CoCrFeNiMo0.5 | - 261 | 7.38 × 10-1 | - 536 | [ |
| Ni-20Cr | - 350.1 | 1.41 × 10-3 | - | [ |
| Ni-40Cr | - 270.6 | 1.35 × 10-4 | - | [ |
Table 5 Corrosion properties of NiCr1.5Mo0.1 alloy coating alongside other alloys reported in literature
| Alloy | Ecorr (mV) | icorr (μA/cm2) | Epp (mV) | References |
|---|---|---|---|---|
| NiCr1.5Mo0.1 | - 185.7 | 4.52 × 10-3 | 101.9 | This work |
| NiCr | - 180.2 | 9.91 × 10-2 | 339.8 | This work |
| Co1.5CrFeNi1.5Ti0.5 | - 443 | 5.7 × 10-1 | - 219 | [ |
| Co1.5CrFeNi1.5Ti0.5Mo0.1 | - 381 | 1.3 × 10-1 | - 215 | [ |
| Co1.5CrFeNi1.5Ti0.5Mo0.5 | - 493 | 2.0 × 10-1 | - 219 | [ |
| Co1.5CrFeNi1.5Ti0.5Mo0.8 | - 551 | 4.1 × 10-1 | - 189 | [ |
| 45# steel | - 601 | 1.028 × 10-2 | - 343 | [ |
| AlCoCr0.5FeNi | - 458 | 7.622 × 10-3 | - 161 | [ |
| AlCoCr0.75FeNi | - 326 | 1.687 × 10-4 | - 276 | [ |
| AlCoCrFeNi | - 270 | 7.113 × 10-5 | - 208 | [ |
| AlCoCr1.5FeNi | - 163 | 2.455 × 10-5 | - 105 | [ |
| AlCoCr2FeNi | - 357 | 3.177 × 10-4 | - 86 | [ |
| 304 SS | - 272 | 1.35 × 10-1 | 132 | [ |
| CoCrFeNiMo0.1 | - 263 | 3.81 × 10-1 | - 638 | [ |
| CoCrFeNiMo0.2 | - 131 | 7.2 × 10-2 | - 661 | [ |
| CoCrFeNiMo0.3 | - 257 | 7.66 × 10-1 | - 656 | [ |
| CoCrFeNiMo0.4 | - 261 | 8.2 × 10-2 | - 576 | [ |
| CoCrFeNiMo0.5 | - 261 | 7.38 × 10-1 | - 536 | [ |
| Ni-20Cr | - 350.1 | 1.41 × 10-3 | - | [ |
| Ni-40Cr | - 270.6 | 1.35 × 10-4 | - | [ |
Fig. 9 Cyclic polarization curves of NiCr, NiCrMo0.1, NiCrMo0.3, NiCr1.5, NiCr1.5Mo0.1, and NiCr1.5Mo0.3 in 3.5 wt% NaCl solution
Fig. 10 EIS plots of samples measured in 3.5 wt% NaCl solution at room temperature: a Nyquist plots, b Bode plots, and c equivalent electrical circuit diagram of NiCrxMoy alloy coatings
| Alloy coatings | Rs (Ω cm2) | R1 (Ω cm2) | R2 (Ω cm2) | CPE1 parameters | CPE2 parameters | ||
|---|---|---|---|---|---|---|---|
| Y0-1 (10-5 Ω-1 cm-2 sn) | n1 | Y0-2 (10-5 Ω-1 cm-2 sn) | n2 | ||||
| NiCr | 15.14 | 9.463 × 105 | 1.460 × 106 | 0.762 | 0.899 | 0.723 | 0.803 |
| NiCrMo0.1 | 13.81 | 1.498 × 106 | 1.912 × 106 | 0.702 | 0.919 | 0.869 | 0.938 |
| NiCrMo0.3 | 16.19 | 2.485 × 105 | 7.323 × 105 | 0.956 | 0.891 | 0.835 | 0.905 |
| NiCr1.5 | 12.62 | 2.640 × 106 | 2.726 × 106 | 0.751 | 0.896 | 0.528 | 0.861 |
| NiCr1.5Mo0.1 | 13.80 | 5.407 × 106 | 5.692 × 106 | 0.668 | 0.862 | 0.472 | 0.825 |
| NiCr1.5Mo0.3 | 14.81 | 7.741 × 103 | 4.868 × 103 | 3.108 | 0.778 | 6.675 | 0.839 |
Table 6 Equivalent circuit parameters obtained by fitting the EIS results of NiCrxMoy alloy coatings in 3.5 wt% NaCl solution at room temperature
| Alloy coatings | Rs (Ω cm2) | R1 (Ω cm2) | R2 (Ω cm2) | CPE1 parameters | CPE2 parameters | ||
|---|---|---|---|---|---|---|---|
| Y0-1 (10-5 Ω-1 cm-2 sn) | n1 | Y0-2 (10-5 Ω-1 cm-2 sn) | n2 | ||||
| NiCr | 15.14 | 9.463 × 105 | 1.460 × 106 | 0.762 | 0.899 | 0.723 | 0.803 |
| NiCrMo0.1 | 13.81 | 1.498 × 106 | 1.912 × 106 | 0.702 | 0.919 | 0.869 | 0.938 |
| NiCrMo0.3 | 16.19 | 2.485 × 105 | 7.323 × 105 | 0.956 | 0.891 | 0.835 | 0.905 |
| NiCr1.5 | 12.62 | 2.640 × 106 | 2.726 × 106 | 0.751 | 0.896 | 0.528 | 0.861 |
| NiCr1.5Mo0.1 | 13.80 | 5.407 × 106 | 5.692 × 106 | 0.668 | 0.862 | 0.472 | 0.825 |
| NiCr1.5Mo0.3 | 14.81 | 7.741 × 103 | 4.868 × 103 | 3.108 | 0.778 | 6.675 | 0.839 |
Fig. 11 Passive film thickness (d) of NiCrxMoy coating in 3.5 wt % NaCl solution at room temperature
Fig. 12 XPS spectra of a O, b Cr, c Mo, d Ni e Fe elements in the passive film on NiCrxMoy (x = 1, 1.5; y = 0, 0.1) alloy coatings after potentiodynamic polarization tests in 3.5 wt% NaCl solution
| Alloy coatings | Peak% | at.% | ||
|---|---|---|---|---|
| NiCr | Cr 2p3/2 | Crox | 54.8 | 8.8 |
| Crhy | 45.2 | |||
| Fe 2p3/2 | Fe2+ | 44.3 | 4.8 | |
| Fe3+ | 55.7 | |||
| Ni 2p3/2 | Ni0 | 8.8 | 2.6 | |
| Niox | 55.1 | |||
| Nihy | 36.1 | |||
| O 1s | O2- | 43.3 | 83.8 | |
| OH- | 35.1 | |||
| H2O | 21.6 | |||
| NiCrMo0.1 | Cr 2p3/2 | Crox | 56.8 | 9.3 |
| Crhy | 43.2 | |||
| Fe 2p3/2 | Fe2+ | 51.5 | 3.4 | |
| Fe3+ | 48.5 | |||
| Ni 2p3/2 | Niox | 79.4 | 3.2 | |
| Nihy | 20.6 | |||
| O 1s | O2- | 36.1 | 82.4 | |
| OH- | 38.5 | |||
| H2O | 25.4 | |||
| Mo 3d5/2 | Mo4+ | 63.3 | 1.7 | |
| Mo6+ | 36.7 | |||
| NiCr1.5 | Cr 2p3/2 | Crox | 60.4 | 11.0 |
| Crhy | 39.6 | |||
| Fe 2p3/2 | Fe2+ | 49.5 | 3.0 | |
| Fe3+ | 50.5 | |||
| Ni 2p3/2 | Ni0 | 11.7 | 1.6 | |
| Niox | 54.9 | |||
| Nihy | 33.4 | |||
| O 1s | O2- | 37.7 | 84.4 | |
| OH- | 41.2 | |||
| H2O | 21.1 | |||
| NiCr1.5Mo0.1 | Cr 2p3/2 | Crox | 57.8 | 11.0 |
| Crhy | 42.2 | |||
| Fe 2p3/2 | Fe2+ | 53.6 | 4.0 | |
| Fe3+ | 46.4 | |||
| Ni 2p3/2 | Niox | 78.1 | 1.5 | |
| Nihy | 21.9 | |||
| O 1s | O2- | 32.8 | 81.8 | |
| OH- | 46.3 | |||
| H2O | 20.9 | |||
| Mo 3d | Mo4+ | 44.8 | 1.6 | |
| Mo6+ | 55.2 | |||
Table 7 Overall composition and percentages from the detailed XPS spectrum of the surface of NiCrxMoy (x = 1, 1.5; y = 0, 0.1) alloy coatings
| Alloy coatings | Peak% | at.% | ||
|---|---|---|---|---|
| NiCr | Cr 2p3/2 | Crox | 54.8 | 8.8 |
| Crhy | 45.2 | |||
| Fe 2p3/2 | Fe2+ | 44.3 | 4.8 | |
| Fe3+ | 55.7 | |||
| Ni 2p3/2 | Ni0 | 8.8 | 2.6 | |
| Niox | 55.1 | |||
| Nihy | 36.1 | |||
| O 1s | O2- | 43.3 | 83.8 | |
| OH- | 35.1 | |||
| H2O | 21.6 | |||
| NiCrMo0.1 | Cr 2p3/2 | Crox | 56.8 | 9.3 |
| Crhy | 43.2 | |||
| Fe 2p3/2 | Fe2+ | 51.5 | 3.4 | |
| Fe3+ | 48.5 | |||
| Ni 2p3/2 | Niox | 79.4 | 3.2 | |
| Nihy | 20.6 | |||
| O 1s | O2- | 36.1 | 82.4 | |
| OH- | 38.5 | |||
| H2O | 25.4 | |||
| Mo 3d5/2 | Mo4+ | 63.3 | 1.7 | |
| Mo6+ | 36.7 | |||
| NiCr1.5 | Cr 2p3/2 | Crox | 60.4 | 11.0 |
| Crhy | 39.6 | |||
| Fe 2p3/2 | Fe2+ | 49.5 | 3.0 | |
| Fe3+ | 50.5 | |||
| Ni 2p3/2 | Ni0 | 11.7 | 1.6 | |
| Niox | 54.9 | |||
| Nihy | 33.4 | |||
| O 1s | O2- | 37.7 | 84.4 | |
| OH- | 41.2 | |||
| H2O | 21.1 | |||
| NiCr1.5Mo0.1 | Cr 2p3/2 | Crox | 57.8 | 11.0 |
| Crhy | 42.2 | |||
| Fe 2p3/2 | Fe2+ | 53.6 | 4.0 | |
| Fe3+ | 46.4 | |||
| Ni 2p3/2 | Niox | 78.1 | 1.5 | |
| Nihy | 21.9 | |||
| O 1s | O2- | 32.8 | 81.8 | |
| OH- | 46.3 | |||
| H2O | 20.9 | |||
| Mo 3d | Mo4+ | 44.8 | 1.6 | |
| Mo6+ | 55.2 | |||
Fig. 13 Microhardness of NiCrxMoy alloy coatings
Fig. 14 a Nanoindentation load-depth curves, b average nanohardness and elastic modulus of the different phases in the NiCr1.5Mo0.1 coating
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