Effect of TiC and TaC additions on the corrosion performance of WC-Co cemented carbides

Abstract

This study investigates the individual and combined effects of adding 12 wt% TiC and 4 wt% TaC on the microstructure and corrosion behavior of WC-8Co cemented carbides. Four material compositions—WC-8Co, WC-8Co-4TaC, WC-8Co-12TiC, and WC-8Co-4TaC-12TiC—were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, electrochemical impedance spectroscopy, potentio-dynamic polarization, potentio-static tests, and Pourbaix diagram analysis. Simultaneous addition of TiC and TaC resulted in significant grain refinement due to the formation of complex (Ti, W)C and (Ta, W)C, with no secondary precipitates observed in the Co binder phase. Electrochemical measurements revealed that WC-8Co-4TaC-12TiC exhibits superior corrosion resistance, achieving a charge transfer resistance (R_p) of 5740 Ω·cm⁻²—substantially higher than that of WC-8Co-12TiC (2220 Ω·cm⁻²), WC-8Co (2134 Ω·cm⁻²), and WC-8Co-4TaC (1051 Ω·cm⁻²). A well-defined passive region (10⁻⁴–10⁻⁵ A/cm⁻²) was observed exclusively in the WC-8Co-4TaC-12TiC alloys, whereas the other alloys underwent active dissolution. Post-corrosion analysis confirmed minimal surface attack and the lowest oxygen content (12 wt%) for WC-8Co-4TaC-12TiC, compared to over 20 wt% for the other compositions. Pourbaix diagram analysis indicated that Ta₂CoO₆ formation in the TaC-modified WC-Co correlates with reduced corrosion resistance, while TiO₂ formation in the TiC composition offers only marginal improvement. Critically, the coexistence of TiO₂ and Ta₂CoO₆ in WC-8Co-4TaC-12TiC leads to a synergistic enhancement in the protectiveness of the surface film. These findings demonstrate that the combined addition of TiC and TaC imparts synergistic benefits through both microstructural refinement and the formation of a complex, protective surface film.

Keywords

WC-Co cemented carbides / TiC/TaC addition / Corrosion performance / Electrochemistry test / Pourbaix diagram

References

[1] Luo L, Lu H, Liu X-m, et al. . Effects of solute elements on mechanical features of WC and Co phases in cemented carbides: High-throughput calculations [J]. International Journal of Refractory Metals and Hard Materials, 2026, 134: 107458

[2] Chen C, Huang B-y, Liu Z-m, et al. . Additive manufacturing of WC-Co cemented carbides: Process, microstructure, and mechanical properties [J]. Additive Manufacturing, 2023, 63: 103410

[3] Raimundo R A, Costa F A, Morales M A, et al. . Understanding the effect of preparation technique and compaction pressure on the microstructure, sinterability and mechanical properties of the Cu-20 wt% WC composite prepared with recycled WC [J]. Journal of Alloys and Compounds Communications, 2025, 6: 100066

[4] Zhou Y-q, Yuan P-h, Xu X-c, et al. . The tribo-corrosion performance of laser powder bed fusion WC/W₂C reinforced stainless steel in different pH value solution [J]. Tribology International, 2025, 206: 110596

[5] Zhou Y-q, Sang K, Wang W-q, et al. . Influence of annealing and tempering on the wear and corrosion behavior of WC/W₂C reinforced composites fabricated by laser powder bed fusion [J]. Tribology International, 2026, 219: 111811

[6] Su Y-f, Wang Y-q, Shi Q, et al. . Effect of treatment process on CVD diamond coatings deposited on WC–Co substrate with different Co contents [J]. Diamond and Related Materials, 2025, 158: 112634

[7] Zhou Y-q, Liu R, Liu H, et al. . Influence of tungsten carbide raw materials to microstructure and wear performance on PTA hard-facing materials with its micromechanism analysis [J]. Surface and Coatings Technology, 2023, 454: 129200

[8] Garcĺa J, Collado ciprés V, Blomqvist A, et al. . Cemented carbide microstructures: A review [J]. International Journal of Refractory Metals and Hard Materials, 2019, 80: 40-68

[9] Cera M, Trudu S, Oumarou A A, et al. . Trends and perspectives in the use of organic acids for critical metal recycling from hard-metal scraps [J]. International Journal of Refractory Metals and Hard Materials, 2023, 114: 106249

[10] Zhou R-x, Liu Z-m, Chen C, et al. . Achieving high mechanical properties of ultrafine-grained WC–Co cemented carbide via material extrusion additive manufacturing [J]. Journal of Materials Science & Technology, 2026, 259: 115-132

[11] Peng Y-b, Zhang W, Li T-c, et al. . Microstructures and wear-resistance of WC-reinforced high entropy alloy composite coatings by plasma cladding: Effect of WC morphology [J]. Surface Engineering, 2021, 37(5): 678-687

[12] Wu Y-c, Lu Z-y, Qin Y-q, et al. . Ultrafine/nano WC-Co cemented carbide: Overview of preparation and key technologies [J]. Journal of Materials Research and Technology, 2023, 27: 5822-5839

[13] Zheng Q-h, Wang W Y, Bolzoni L, et al. . Interface phonon transmission behaviors and their resultant influence on thermal transport in Cu/diamond composites [J]. Materials Genome Engineering Advances, 2026, 4(2): e70069

[14] Mao P, Peng J-f, Chen K, et al. . Effect of deep cryogenic treatment on the mechanical properties of ultrafine WC-Co composite [J]. International Journal of Refractory Metals and Hard Materials, 2026, 134: 107429

[15] Sten S, Odqvist J, Norgren S, et al. . Development of a functional hardness gradient in WC-TiC-Co cemented carbide during gradient sintering [J]. International Journal of Refractory Metals and Hard Materials, 2023, 115: 106293

[16] Wang B-x, Qi X-y, Zhang D-q, et al. . High-hardness and toughness-retaining ultrafine WC-Co cemented carbides: Microstructure, mechanical properties, and parameter optimization [J]. International Journal of Refractory Metals and Hard Materials, 2026, 136: 107648

[17] Van Der Merwe R, Sacks N. Effect of TaC and TiC on the friction and dry sliding wear of WC–6wt.% Co cemented carbides against steel counterfaces [J]. International Journal of Refractory Metals and Hard Materials, 2013, 41: 94-102

[18] Huang S-w, Xiong J, Guo Z-x, et al. . Oxidation of WC-TiC-TaC-Co hard materials at relatively low temperature [J]. International Journal of Refractory Metals and Hard Materials, 2015, 48: 134-140

[19] Su B-h, Li J, Wang W Y, et al. . Effects of transition metals (TM = Nb, Ta, and Zr) on thermodynamic and electronic properties of advanced (Th, _1−xTM_x)C (x = 0.1 and 0.2) fuels: A first-principles study [J]. Materials Genome Engineering Advances, 2026, 4: e70052

[20] Buravlev I Y, Shichalin O O, Belov A A, et al. . Microstructural evolution and mechanical behavior of WC–4wt.% TiC–3wt.% TaC–12wt.% Co refractory cermet consolidated by spark plasma sintering of mechanically activated powder mixtures [J]. Advanced Powder Technology, 2024, 35(10): 104625

[21] Hou B-r, Li X-g, Ma X-m, et al. . The cost of corrosion in China [J]. npj Materials Degradation, 2017, 1: 4

[22] Zhou Y-q, Wang S-y, Feng S-k, et al. . Unveiling the influence of gravity on pitting corrosion through advanced high-throughput corrosion test method [J]. Materials Genome Engineering Advances, 2025, 3(4): e70038

[23] Zhou Y-q, Engelberg D L. Development of a two-dimensional bipolar electrochemistry technique for high throughput corrosion screening [J]. Materials Genome Engineering Advances, 2024, 2(3): e57

[24] Zhou Q-q, Wang Q-w, Yang L, et al. . Investigating CMAS corrosion in ultrahigh temperature Hf₆Ta₂O₁₇-based thermal barrier coatings: A mechanism by which corrosion products hinder corrosion resistance [J]. Materials Genome Engineering Advances, 2025, 3(4): e70018

[25] Zhu Y-k, Zhang L, Yang R, et al. . Artificial intelligence-enabled synergistic design of strength and stress corrosion cracking resistance in light alloys [J]. Materials Genome Engineering Advances, 2025, 3(4): e70039

[26] Zhou Y-q, Li Y-h, Zhao J-x, et al. . Microstructure, mechanical and corrosion performance of TiC steel-bonded carbides with different heat treatments [J]. International Journal of Refractory Metals and Hard Materials, 2025, 128: 107061

[27] Zhou Y-q, Engelberg D L. Fast testing of ambient temperature pitting corrosion in type 2205 duplex stainless steel by bipolar electrochemistry experiments [J]. Electrochemistry Communications, 2020, 117: 106779

[28] Zhou Y-q, Huang Z-y, Kong D-c, et al. . Applying bipolar electrochemistry to assess the corrosion mechanism of HVOF WC-based coatings with varies binders in different environments [J]. Surface and Coatings Technology, 2024, 477: 130252

[29] Kellner F J J, Killian M S, Yang G, et al. . TEM and ToF-SIMS studies on the corrosion behavior of vanadium and chromium containing WC–Co hard metals in alkaline solutions [J]. International Journal of Refractory Metals and Hard Materials, 2011, 29(3): 376-383

[30] Zhang X, Zhou J-h, Liu C, et al. . Effects of Ni addition on mechanical properties and corrosion behaviors of coarse-grained WC-10(Co, Ni) cemented carbides [J]. International Journal of Refractory Metals and Hard Materials, 2019, 80: 123-129

[31] Badawy W A, Al-Kharafi F M. Corrosion and passivation behaviors of molybdenum in aqueous solutions of different pH [J]. Electrochimica Acta, 1998, 44(4): 693-702

[32] Guo S-d, Bao R, Li S-y, et al. . The role of Y₂O₃, Cu, Mo and Mo2C additives on optimizing the corrosion resistance of WC-6Co cemented carbide in HCl and NaOH solutions [J]. Journal of Alloys and Compounds, 2020, 827: 154269

[33] Imasato S, Sakaguchi S, Okada T, et al. . Effect of WC grain size on corrosion resistance of WC-Co cemented carbide [J]. Journal of the Japan Society of Powder and Powder Metallurgy, 2001, 48(7): 609-615

[34] Zhou Y-q, Liu Y-k, Wang S-y, et al. . The corrosion performance for ultrafine WC-¹²Co processed by heat treatments in different pH solutions [J]. International Journal of Refractory Metals and Hard Materials, 2024, 125: 106878

[35] Zhang L, Chen Y, Wan Q-l, et al. . Electrochemical corrosion behaviors of straight WC–Co alloys: Exclusive variation in grain sizes and aggressive media [J]. International Journal of Refractory Metals and Hard Materials, 2016, 57: 70-77

[36] Lin N, He Y-h, Wu C-h, et al. . Influence of TiC additions on the corrosion behaviour of WC–Co hardmetals in alkaline solution [J]. International Journal of Refractory Metals and Hard Materials, 2014, 46: 52-57

[37] Myalska H, Michalska J K, Moskal G, et al. . Effect of nano-sized TiC powder on microstructure and the corrosion resistance of WC-Co thermal spray coatings [J]. Surface and Coatings Technology, 2017, 318: 270-278

[38] Zhu B-s, Zhang S-f, Zheng L-y, et al. . Influence of TaC on structure, mechanical, corrosion and wear performances of WC-5Co cemented carbide [J]. Ceramics International, 2025, 51(16): 21621-21631

[39] Zhai X-x, Lu K-h, Peng C, et al. . Effects of Nb/TiC/TaC/VC and Co addition on the microstructure and properties of WC-based cemented carbides [J]. International Journal of Applied Ceramic Technology, 2023, 20(5): 2785-2795

[40] Chen Z-w, Wang Z-h, Wang B-x, et al. . Microstructure and properties of WC-8Co cemented carbides prepared by multiple spark plasma sintering [J]. International Journal of Applied Ceramic Technology, 2021, 18(6): 2010-2019

[41] Anwer Z, Huang S-g, Vleugels J. Liquid phase assisted synthesis of (Ti, V, Nb, Ta, W)C-Ni high entropy carbide cermets by conventional pressureless sintering [J]. International Journal of Refractory Metals and Hard Materials, 2022, 107: 105914

[42] Jin X-z, Luo H, Wang X-f, et al. . Data mining accelerated the design strategy of high-entropy alloys with the largest hardness based on genetic algorithm optimization [J]. Materials Genome Engineering Advances, 2024, 2(2): e49

[43] Qiao Q, Liu Q, Pu J, et al. . A comparative study of machine learning in predicting the mechanical properties of the deposited AA6061 alloys via additive friction stir deposition [J]. Materials Genome Engineering Advances, 2024, 2: e31

[44] Meng H-y, Huang J, Zhao T-h, et al. . High-throughput assessment of Nb, Co, Ti, and Al effects on microstructure and mechanical properties in wrought nickel-based superalloys [J]. Materials Genome Engineering Advances, 2025, 3(3): e70002

[45] Li J-l, Hughes A E, Yang Y S, et al. . Quantitative 3D characterization for kinetics of corrosion initiation and propagation in additively manufactured austenitic stainless steel [J]. Advanced Science, 2022, 9(36): 2201162

[46] Zhou Y-q, Engelberg D L. Time-lapse observation of pitting corrosion in ferritic stainless steel under bipolar electrochemistry control [J]. Journal of Electroanalytical Chemistry, 2021, 899: 115599

[47] Zhou Y-q, Liu Y-k, Huang Z-y, et al. . Microstructure, wear, and corrosion performance of spherical cast tungsten carbide reinforced stainless steel-based composites manufactured by plasma transferred arc techniques [J]. Vacuum, 2025, 233: 114003

[48] Zhou Y-q, Kong D-c, Wang L, et al. . Pit growth kinetics of additively manufactured MoNi over-alloyed type 316L stainless steel [J]. Journal of Materials Research and Technology, 2023, 27: 7532-7547

[49] Zhou Y-q, Engelberg D L. Accessing the full spectrum of corrosion behaviour of tempered type 420 stainless steel [J]. Materials and Corrosion, 2021, 72(11): 1718-1729

[50] Wang L, Dong C-f, Man C, et al. . Enhancing the corrosion resistance of selective laser melted 15–5PH martensite stainless steel via heat treatment [J]. Corrosion Science, 2020, 166: 108427

[51] Fu Y, Luo H, Chen X-r, et al. . The corrosion behavior and passive film properties of the cast and annealed AlCoCrFeNi_2.1 eutectic high-entropy alloy in sulfuric acid solution [J]. Corrosion Science, 2024, 240: 112456

[52] Marcelin S, Pébère N, Régnier S. Electrochemical characterisation of a martensitic stainless steel in a neutral chloride solution [J]. Electrochimica Acta, 2013, 87: 32-40

[53] Li Z-j, Luo H, Hou L-f, et al. . Effect of Mn addition on the corrosion behavior of FeCrNiMn Si alloys in simulated seawater environment [J]. Corrosion Science, 2025, 252: 112978

[54] El-Shater R, Sad N I A, Abdel-Khalek E K, et al. . Syenthis, structural, magnetic, optical, and dielectric properties of ag and cr substituted co-ferrite nanoparticles [J]. Scientific Reports, 2025, 15: 38493

[55] Ren L-l, Wang L-h, Qin Y-f, et al. . High cycle stability of hybridized co(OH)₂ nanomaterial structures synthesized by the water bath method as anodes for lithium-ion batteries [J]. Micromachines, 2022, 13(2): 149

[56] Tang T-t, Xiao X-l, Xu K, et al. . Corrosion-resistant WC-Co based cemented carbides: Computational design and experimental verification [J]. International Journal of Refractory Metals and Hard Materials, 2023, 110: 106044

[57] Chai C, Liu J-x, Wang Y-w, et al. . Enhancement in photocatalytic performance of Ag–AgCl decorated with h-WO₃ and mechanism insight [J]. Applied Physics A, 2019, 125(2): 96

[58] Wang F, Liu Y, Wei H-j, et al. . Graphene induced growth of Sb₂WO₆ nanosheets for high-performance pseudocapacitive lithium-ion storage [J]. Journal of Alloys and Compounds, 2020, 839: 155614

[59] Zhou Y-q, Wang W-q, Sang K, et al. . Electrochemical corrosion of cemented carbides: Mechanisms, mitigation strategies, characterization techniques, and future directions [J]. Review of Materials Research, 2026, 2(2): 100169

[60] Materer N F, Apblett A, Kadossov E B, et al. . The preparation and chemical reaction kinetics of tungsten bronze thin films and nitrobenzene with and without a catalyst [J]. Surface Science, 2016, 648: 345-351

[61] Ospina R, Arango P, Arango Y C, et al. . Study of W/WC films produced by plasma assisted vacuum arc discharge [J]. Physica Status Solidi (c), 2005, 2(10): 3758-3761

[62] Zhou Y-q, Yang Z-g, Zhang C. Synergistic Mo and N effects on pitting corrosion of lean duplex stainless steels: A fundamental shift in phase-dependent stability in halide environments [J]. Corrosion Science, 2026, 260: 113556

[63] Vignal V, Krawiec H, Heintz O, et al. . Passive properties of lean duplex stainless steels after long-term ageing in air studied using EBSD, AES, XPS and local electrochemical impedance spectroscopy [J]. Corrosion Science, 2013, 67: 109-117

[64] Vázquez-Pelayo A, Garcia-Mendoza T, Becerril-Juarez I G, et al. . Mechanosynthesis of TaC-WC powders under environmental conditions and their consolidation via electric arc furnace [J]. Materials Research Express, 2024, 11(6): 065601

[65] Wu C-z, Qi R-f, Zhang X, et al. . Quick mass-production of MAX (Ti₂AlC) book with pages separated by stacking faults benefiting removal of “a” layer [J]. Chemical Communications, 2019, 55(52): 7522-7525

[66] Aguinaco A, Amaya B, Ramírez-del-solar M. Facile fabrication of Fe-TiO₂ thin film and its photocatalytic activity [J]. Environmental Science and Pollution Research, 2022, 29(16): 23292-23302

[67] Wang Z-b, Guo X-y, Montoya J, et al. . Predicting aqueous stability of solid with computed Pourbaix diagram using SCAN functional [J]. npj Computational Materials, 2020, 6: 160

[68] Xiao X-l, Chang K-k, Xu K, et al. . Efficient prediction of corrosion behavior in ternary Ni-based alloy systems: Theoretical calculations and experimental verification [J]. Journal of Materials Science & Technology, 2023, 167: 94-106

[69] Chen D-h, Zhou W-j, Ji Y-c, et al. . Applications of density functional theory to corrosion and corrosion prevention of metals: A review [J]. Materials Genome Engineering Advances, 2025, 3: e83

[70] Sang S-w, Zhang K-y, Yin L-c, et al. . Machine learning-accelerated computational screening of CrNiCu ternary alloy as superior cocatalyst for photocatalytic hydrogen evolution [J]. Materials Genome Engineering Advances, 2025, 3(2): e70014

[71] Jiang Y, Li J-s, Yang X, et al. . Applications of generative adversarial networks in materials science [J]. Materials Genome Engineering Advances, 2024, 2: e30

[72] Ong S P, Richards W D, Jain A, et al. . Python Materials Genomics (pymatgen): A robust, open-source Python library for materials analysis [J]. Computational Materials Science, 2013, 68: 314-319

[73] Liu Y-f, Tran H, Huang C-f, et al. . Accelerated predictions of the sublimation enthalpy of organic materials with machine learning [J]. Materials Genome Engineering Advances, 2025, 3: e84

[74] Jain A, Ong S P, Hautier G, et al. . Commentary: The Materials Project: A materials genome approach to accelerating materials innovation [J]. APL Materials, 2013, 1: 011002

[75] Lv S, Peng L, Wu W-t, et al. . Bridging language models and computational materials science: A prompt-driven framework for material property prediction [J]. Materials Genome Engineering Advances, 2025, 3(2): e70013

[76] Xu K, Bu H-k, Pan S-n, et al. . GPUMD 4.0: A high-performance molecular dynamics package for versatile materials simulations with machine-learned potentials [J]. Materials Genome Engineering Advances, 2025, 3(3): e70028

RIGHTS & PERMISSIONS

Central South University

Just Accepted

This article has successfully passed peer review and final editorial review, and will soon enter typesetting, proofreading and other publishing processes. The currently displayed version is the accepted final manuscript. The officially published version will be updated with format, DOI and citation information upon launch. We recommend that you pay attention to subsequent journal notifications and preferentially cite the officially published version. Thank you for your support and cooperation.