Anisotropic pitting mechanisms during the electropolishing of bulk metallic glass surfaces in a chloride-containing non-aqueous solution

Shun-Hua Chen , Jia-Yao Chen , Xiao-Kang Yue , Jun-Sheng Zhang , Huo-Hong Tang

Advances in Manufacturing ›› 2026, Vol. 14 ›› Issue (3) : 598 -619.

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Advances in Manufacturing ›› 2026, Vol. 14 ›› Issue (3) :598 -619. DOI: 10.1007/s40436-025-00565-w
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Anisotropic pitting mechanisms during the electropolishing of bulk metallic glass surfaces in a chloride-containing non-aqueous solution
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Abstract

Anisotropic pitting mechanisms were investigated during electropolishing (EP) of Zr-based bulk metallic glass (BMG) surfaces in a chloride-containing alcohol-based electrolyte. Electrically discharge-machined (EDMed) and mechanically polished (MPed) BMG surfaces were selected as the typical preprocessing surfaces. NaCl-ethylene glycol solution was selected as the electrolyte because of its ability to avoid solvent decomposition and form high-viscosity complexes on surfaces to lower the surface roughness. The surface roughness and morphology of both specimens under varying EP parameters were examined and compared. With the optimized parameters, the recast layer of the EDMed surface was removed, and a decrease of more than 50% in the roughness values was achieved for both types of surfaces. However, anisotropic pitting also occurred on the surfaces subjected to EP. Further findings showed that pitting was induced by the notches distributed in the Cu-rich film covering the EPed surfaces, which resulted from the distinctive dissolution rates of different elements. For the EDMed surface, the notches were related to the Zr-rich crystals observed beneath the recast layer, whereas for the MPed surfaces, such notches appeared directly during the gradual dissolution of the surfaces. The Cu2O product serving as a protective layer for the covered region was detected at the pitting boundary on both types of surfaces. The region without such protection gradually dissolves at high voltages. In addition, deep slots were formed at the boundaries of the pits on the MPed surfaces under the corrosion of chloride ions, which were concentrated at the boundaries. Finally, dissolution-pitting models were proposed to describe the anisotropic pitting mechanisms on BMG surfaces in non-aqueous solutions.

Keywords

Electropolishing (EP) / Bulk metallic glass / Electrically discharge-machine (EDM) / NaCl-ethylene glycol / Pitting mechanism

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Shun-Hua Chen, Jia-Yao Chen, Xiao-Kang Yue, Jun-Sheng Zhang, Huo-Hong Tang. Anisotropic pitting mechanisms during the electropolishing of bulk metallic glass surfaces in a chloride-containing non-aqueous solution. Advances in Manufacturing, 2026, 14 (3) : 598-619 DOI:10.1007/s40436-025-00565-w

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References

[1]

Klement W, Willens RH, Duwez POL. Non-crystalline structure in solidified gold-silicon alloys. Nature, 1960, 187: 869-870

[2]

Wang WH, Dong C, Shek CH. Bulk metallic glasses. Mater Sci Eng R, 2004, 44: 45-89

[3]

Inoue A, Nishiyama N. New bulk metallic glasses for applications as magnetic-sensing, chemical, and structural materials. MRS Bull, 2007, 32: 651-658

[4]

Li N, Chen W, Liu L. Thermoplastic micro-forming of bulk metallic glasses: a review. JOM, 2016, 68: 1246-1261

[5]

Yan W, Richard I, Kurtuldu G, et al. . Structured nanoscale metallic glass fibres with extreme aspect ratios. Nat Nanotechnol, 2020, 15: 875-882

[6]

Aliyu AAA, Panwisawas C, Shinjo J, et al. . Laser-based additive manufacturing of bulk metallic glasses: recent advances and future perspectives for biomedical applications. J Mater Res Technol, 2023, 23: 2956-2990

[7]

Wang T, Wu XY, Zhang GQ, et al. . Study on surface roughness and top burr of micro-milled Zr-based bulk metallic glass in shear dominant zone. Int J Adv Manuf Technol, 2020, 107: 4287-4299

[8]

Gong YD, Liu Y, Sun Y, et al. . Experimental and emulational investigations into grinding characteristics of Zr-based bulk metallic glass (BMG) using microgrinding. Int J Adv Manuf Technol, 2018, 97: 3431-3451

[9]

Chau SY, To S, Sun ZW, et al. . Twinned-serrated chip formation with minor shear bands in ultra-precision micro-cutting of bulk metallic glass. Int J Adv Manuf Technol, 2020, 107: 4437-4448

[10]

Yang HD, Wu YS, Zhang JS, et al. . Study on the cutting characteristics of high-speed machining Zr-based bulk metallic glass. Int J Adv Manuf Technol, 2022, 119: 3533-3544

[11]

Chen SH, Ge Q, Zhang JS, et al. . Low-speed machining of a Zr-based bulk metallic glass. J Manuf Process, 2021, 72: 565-581

[12]

Sueptitz R, Horn S, Stoica M, et al. . Electrochemical micromachining of passive electrodes: application to bulk metallic glasses. J Mater Process Technol, 2015, 219: 193-198

[13]

Chen SH, Gu HW, Feng KK, et al. . A comparative study on the die-sinking EDM performance of bulk metallic glass composites under rough and refined conditions. Int J Adv Manuf Technol, 2022, 121: 4865-4883

[14]

Chen SH, Gu HW, Wang JY, et al. . Processing of monolithic bulk metallic glass using sinking electrical discharge machining. Int J Adv Manuf Technol, 2023, 126: 5057-5080

[15]

Tang HH, Li XB, Meng L, et al. . Process modeling and optimization in laser drilling of bulk metallic glasses based on GABPNN and machine vision. Opt Laser Technol, 2024, 172: 110502

[16]

Wang J, Chen W, Han FZ. Study on the magnetorheological finishing method for the WEDMed pierced die cavity. Int J Adv Manuf Technol, 2015, 76: 1969-1975

[17]

Zhang TL, Yuan H, Cai M. Effects of recast layer on fatigue performance of laser-drilled holes in nickel-based superalloy. J Mater Process Technol, 2023, 311: 117821

[18]

Deng CB, Jiang L, Qin N, et al. . Effects of pH and H2O2 on the chemical mechanical polishing of titanium alloys. J Mater Process Technol, 2021, 295: 117204

[19]

Han W, Fang FZ. Fundamental aspects and recent developments in electropolishing. Int J Mach Tools Manuf, 2019, 139: 1-23

[20]

Park CG, Son BH, Kwak JS. A study on deburring process of micro channel using EP and MAP hybrid process. Adv Mater Res, 2013, 741: 39-44

[21]

Zhang BC, Lee XH, Bai JM, et al. . Study of selective laser melting (SLM) Inconel 718 part surface improvement by electrochemical polishing. Mater Des, 2017, 116: 531-537

[22]

Winiarski J, Tylus W, Pawlyta M, et al. . Titanium anodization in deep eutectic solvents: the effect of anodizing time on the morphology and structure of anodic layers. Appl Surf Sci, 2022, 577: 151892

[23]

Zaki S, Guan T, Zhang N, et al. . Precision shaping of nickel micro-mould features via electropolishing: characterisation of electrolytes from strong to weak acids. J Manuf Process, 2024, 113: 261-274

[24]

Zaki S, Zhang N, Gilchrist MD. Microscale shaping and rounding of ridge arrays and star pattern features on nickel mould via electrochemical polishing. Adv Manuf, 2024, 12: 207-226

[25]

Ramasawmy H, Blunt L. 3D surface characterisation of electropolished EDMed surface and quantitative assessment of process variables using Taguchi methodology. Int J Mach Tools Manuf, 2002, 42: 1129-1133

[26]

Richter C, Krah T, Buettgenbach S. Novel 3D manufacturing method combining microelectrial discharge machining and electrochemical polishing. Microsyst Technol, 2012, 18: 1109-1118

[27]

Kumar A, Mahanti R, Das M. Electropolishing of thin-cruciform gimbal flexure of gyroscope fabricated by electrical discharge machining. Mater Manuf Process, 2022, 38: 1307-1319

[28]

Kumar A, Mahanti R, Das M. Investigation of electropolishing performance on surface residual stress and morphology of electrical discharge machined maraging steel. Proc Inst Mech Eng Part C-J Eng Mech Eng Sci, 2024, 238: 3215-3225

[29]

Landolt D. Fundamental aspects of electropolishing. Electrochim Acta, 1987, 32: 1-11

[30]

Fushimi K, Habazaki H. Anodic dissolution of titanium in NaCl-containing ethylene glycol. Electrochim Acta, 2008, 53: 3371-3376

[31]

Fushimi K, Kondo H, Konno H. Anodic dissolution of titanium in chloride-containing ethylene glycol solution. Electrochim Acta, 2009, 55: 258-264

[32]

Liu WD, Luo Z, Kunieda M. Electrolyte jet machining of Ti1023 titanium alloy using NaCl ethylene glycol-based electrolyte. J Mater Process Technol, 2020, 283: 116731

[33]

Guo C, Wu B, Xu B, et al. . Electrochemical surface smoothing of spark erosion treated Zr-based bulk metallic glasses in NaCl-ethylene glycol electrolyte. Int J Adv Manuf Technol, 2021, 116: 1591-1607

[34]

Kawashima A, Ohmura K, Yokoyama Y, et al. . The corrosion behaviour of Zr-based bulk metallic glasses in 0.5M NaCl solution. Corros Sci, 2011, 53: 2778-2784

[35]

Hua NB, Huang L, Wang JF, et al. . Corrosion behavior and in vitro biocompatibility of Zr-Al-Co-Ag bulk metallic glasses: an experimental case study. J Non-Cryst Solids, 2012, 358: 1599-1604

[36]

Mudali UK, Baunack S, Eckert J, et al. . Pitting corrosion of bulk glass-forming zirconium-based alloys. J Alloys Compd, 2004, 377: 290-297

[37]

Qiu ZWJ, Li ZK, Fu HM, et al. . Corrosion mechanisms of Zr-based bulk metallic glass in NaF and NaCl solutions. J Mater Sci Technol, 2020, 46: 33-43

[38]

Green BA, Steward RV, Kim I, et al. . In situ observation of pitting corrosion of the Zr50Cu40Al10 bulk metallic glass. Intermetallics, 2009, 17: 568-571

[39]

Nie XP, Yang XH, Jiang JZ. Ti microalloying effect on corrosion resistance and thermal stability of CuZr-based bulk metallic glasses. J Alloys Compd, 2009, 481: 498-502

[40]

Qin CL, Asami K, Zhang T, et al. . Corrosion behavior of Cu-Zr-Ti-Nb bulk glassy alloys. Mater Trans, 2003, 44: 749-753

[41]

Chen SH, Peng XF, Gu HW, et al. . Electropolishing of complex-shaped bulk metallic glasses in NaCl-ethylene glycol electrolyte. Mater Today Commun, 2024, 40: 109630

[42]

Zhou XY, Wang F, Zhang XQ, et al. . Electrochemical polishing of microfluidic moulds made of tungsten using a bi-layer electrolyte. J Mater Process Technol, 2021, 292: 117055

[43]

Hang YS, Yang T, Xu ZY, et al. . Electrochemical micromachining of ZrCu-based amorphous alloy in ethylene glycol solution. Intermetallics, 2021, 132: 107155

[44]

Yi R, Ji JW, Zhan ZJ, et al. . Mechanism study of electropolishing from the perspective of etching isotropy. J Mater Process Technol, 2022, 305: 117599

[45]

Wang F, Zhang XQ, Deng H. A comprehensive study on electrochemical polishing of tungsten. Appl Surf Sci, 2019, 475: 587-597

[46]

Hoar TP, Mears DC, Rothwell GP. The relationships between anodic passivity, brightening and pitting. Corros Sci, 1965, 5: 279-289

[47]

Neufeld P, Southall D. Gas evolution and pitting in electropolishing. Trans Inst Met Finish, 1976, 54: 40-44

[48]

Han W, Fang FZ. Investigation of electropolishing characteristics of tungsten in eco-friendly sodium hydroxide aqueous solution. Adv Manuf, 2020, 8: 265-278

[49]

Sahu S, Swanson OJ, Li T, et al. . Localized corrosion behavior of non-equiatomic NiFeCrMnCo multi-principal element alloys. Electrochim Acta, 2020, 354: 136749

[50]

Yasuda M, Weinberg F, Tromans D. Pitting corrosion of Al and Al-Cu single crystals. J Electrochem Soc, 1990, 137: 3708

[51]

Xia C, Feng Z, Liu S, et al. . Anisotropic pitting of single-phase β-Zr alloy and isotropic pitting of α+β double-phase Zr alloy. Corros Sci, 2017, 127: 39-44

[52]

Yang G, Wang B, Tawfiq K, et al. . Electropolishing of surfaces: theory and applications. Surf Eng, 2017, 33: 149-166

[53]

Piotrowski O, Madore C, Landolt D. The mechanism of electropolishing of titanium in methanol-sulfuric acid electrolytes. J Electrochem Soc, 1998, 145: 2362

[54]

Hamann CH, Hamnett A, Vielstich W (2007) Electrochemistry, 2nd completely revised and updated edition. WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

[55]

Han W, Fang FZ. Two-step electropolishing of 316L stainless steel in a sulfuric acid-free electrolyte. J Mater Process Technol, 2020, 279: 116558

[56]

Yang XD, Han X, Zhou F, et al. . Molecular dynamics simulation of residual stress generated in EDM. Procedia CIRP, 2013, 6: 432-437

[57]

Liu WD, Zhang H, Luo Z, et al. . Electrochemical micromachining on titanium using the NaCl-containing ethylene glycol electrolyte. J Mater Process Technol, 2018, 255: 784-794

[58]

Wang CC, Chow HM, Yang LD, et al. . Recast layer removal after electrical discharge machining via Taguchi analysis: a feasibility study. J Mater Process Technol, 2009, 209: 4134-4140

[59]

Choi SH, Kim BH, Shin HS, et al. . Analysis of the electrochemical behaviors of WC-Co alloy for micro ECM. J Mater Process Technol, 2013, 213: 621-630

[60]

Sethi A, Acharya BR, Saha P. Electrochemical dissolution of WC-Co micro-tool in micro-WECM using an eco-friendly citric acid mixed NaNO3 electrolyte. J Electrochem Soc, 2022, 169: 033503

[61]

Lohrengel MM, Rataj KP, Schubert N, et al. . Electrochemical machining of hard metals-WC/Co as example. Powder Metall, 2014, 57: 21-30

[62]

Zuo HY, Gong M, Zheng XW, et al. . Corrosion behavior of 3A21 aluminum alloy in ethylene glycol solution under different atmospheres. Mater Res Express, 2020, 7: 026523

[63]

Zhang YF, Li JZ, Che SH, et al. . Electrochemical polishing of additively manufactured Ti-6Al-4V alloy. Met Mater Int, 2020, 26: 783-792

[64]

Ferreri NC, Savage DJ, Knezevic M. Non-acid, alcohol-based electropolishing enables high-quality electron backscatter diffraction characterization of titanium and its alloys: application to pure Ti and Ti-6Al-4V. Mater Charact, 2020, 166: 110406

[65]

Niu L, Cheng YF. Electrochemical characterization of metastable pitting of 3003 aluminum alloy in ethylene glycol-water solution. J Mater Sci, 2007, 42: 8613-8617

[66]

Paillier J, Mickel C, Gostin PF, et al. . Characterization of corrosion phenomena of Zr-Ti-Cu-Al-Ni metallic glass by SEM and TEM. Mater Charact, 2010, 61: 1000-1008

[67]

Wolff U, Gebert A, Eckert J, et al. . Effect of surface pretreatment on the electrochemical activity of a glass-forming Zr-Ti-Al-Cu-Ni alloy. J Alloys Compd, 2002, 346: 222-229

[68]

Homazava N, Suter T, Schmutz P, et al. . Online hyphenation of potentiostat to a microflow-capillary FI-ICP-MS for simultaneous in situ electrochemical, time and element resolved characterization of local corrosion processes—an application for Zr-bulk metallic glass. J Anal At Spectrom, 2009, 24: 1161-1169

[69]

Haynes WM. CRC handbook of chemistry and physics, 201495Boca Raton, CRC Press

[70]

Long JL, Dong JG, Wang XX, et al. . Photochemical synthesis of submicron- and nano-scale Cu2O particles. J Colloid Interface Sci, 2009, 333: 791-799

[71]

Huang L, Peng F, Wang HJ, et al. . Preparation and characterization of Cu2O/TiO2 nano-nano heterostructure photocatalysts. Catal Commun, 2009, 10: 1839-1843

[72]

Jia WZ, Guo M, Zheng Z, et al. . Vertically aligned CuO nanowires based electrode for amperometric detection of hydrogen peroxide. Electroanalysis, 2008, 20: 2153-2157

[73]

Volanti DP, Keyson D, Cavalcante LS, et al. . Synthesis and characterization of CuO flower-nanostructure processing by a domestic hydrothermal microwave. J Alloys Compd, 2008, 459: 537-542

[74]

Debbichi L, Marco de Lucas MC, Pierson JF, et al. . Vibrational properties of CuO and Cu4O3 from first-principles calculations, and Raman and infrared spectroscopy. J Phys Chem C, 2012, 116: 10232-10237

[75]

Sun D, Yin PG, Guo L. Synthesis and Raman property of porous jujube-like Cu2O hierarchy structure. Acta Phys Chim Sin, 2011, 27: 1543-1550

[76]

Chai MX, Li ZY, Yan HJ, et al. . Flow field characteristics analysis of interelectrode gap in electrochemical machining of film cooling holes. Int J Adv Manuf Technol, 2021, 112: 525-536

[77]

Jia JL, Xu J, Ma BJ, et al. . Flow field and temperature field analysis of three-sided feed cathode for deep special-shaped hole in ECM. Int J Adv Manuf Technol, 2023, 127: 5897-5913

[78]

Samin AJ, Taylor CD. A combined density functional theory and Monte Carlo investigation of the competitive adsorption of atomic oxygen and chlorine to the Ni (111) Surface. J Electrochem Soc, 2018, 165: C302-C309

[79]

Feng ZC, Cheng XQ, Dong CF, et al. . Effects of dissolved oxygen on electrochemical and semiconductor properties of 316L stainless steel. J Nucl Mater, 2010, 407: 171-177

[80]

Kim DH, Son KS, Sung DH, et al. . Effect of added ethanol in ethylene glycol-NaCl electrolyte on titanium electropolishing. Corros Sci, 2015, 98: 494-499

[81]

Xiao XY, Liu XH, Wang ZL, et al. . Corrosion mechanism and corrosion behavior prediction of Cu-10Ni-X alloys in NaCl solution combining DFT calculation and experiments. Corros Sci, 2024, 227: 111671

[82]

Kawashima A, Asami K, Hashimoto K. An XPS study of anodic behaviour of amorphous nickel-phosphorus alloys containing chromium, molybdenum or tungsten in 1 M HCl. Corros Sci, 1984, 24: 807-823

[83]

Hiromoto S, Asami K, Tsai AP, et al. . Surface characterization of amorphous Zr-Al-(Ni, Cu) alloys immersed in cell-culture medium. Mater Trans, 2002, 43: 261-266

Funding

Anhui Provincial Natural Science Foundation(2308085ME172)

Fundamental Research Funds for the Central Universities of China(JZ2024HGTA0173)

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Shanghai University and Periodicals Agency of Shanghai University and Springer-Verlag GmbH Germany, part of Springer Nature

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