This study introduces a newly developed Ti-based amorphous alloy with enhanced corrosion resistance, tailored for harsh environments. By replacing Hf with misch metal elements (Ce and La) in Ti41.5Zr2.5Hf5Cu42.5Ni7.5Si1, the new alloy demonstrated superior glass forming abilities, including the largest supercooled liquidus region (ΔT) of 35.75 °C and the highest enthalpy change (ΔH) of 135.19 J/g. Furthermore, this new alloy exhibited exceptional corrosion resistance, with 200 times minimized mass loss in 10% HCl compared to its Ti41.5Zr2.5Hf5Cu42.5Ni7.5Si1 counterpart, significantly outperforming conventional crystalline and other amorphous Ti alloys. Furthermore, smaller powders (<25 μm), produced under higher cooling rates, retained their amorphous structure and showed optimal performance, highlighting the critical role of particle size in ensuring consistent properties. These results establish the new alloy as a promising material for advanced applications requiring superior durability and manufacturability.
HaoYLLiSJSunBB, et al.Ductile titanium alloy with low poisson’s ratio. Phys Rev Lett2007; 98: 216405.
2.
YangJSongYDongK, et al.Research progress on the corrosion behavior of titanium alloys. Corros Rev2023; 41: 5–20.
3.
BarbasABonnetASLipinskiP, et al.Development and mechanical characterization of porous titanium bone substitutes. J Mech Behav Biomed2012; 9: 34–44.
4.
AttarHCalinMZhangLC, et al.Manufacture by selective laser melting and mechanical behavior of commercially pure titanium. Mat Sci Eng A2014; 593: 170–177.
5.
SohnHS. Current status of titanium smelting technology for powder metallurgy. J Kor Powd Met Inst2021; 28: 164–172.
6.
FukudaATakemotoMSaitoT, et al.Osteoinduction of porous Ti implants with a channel structure fabricated by selective laser melting. Acta Biomater2011; 7: 2327–2336.
7.
StampRFoxPO’NeillW, et al.The development of a scanning strategy for the manufacture of porous biomaterials by selective laser melting. J Mater Sci Mater Med2009; 20: 1839–1848.
8.
ZhangLCSercombeTB. Selective laser melting of low-modulus biomedical Ti-24Nb-4Zr-8Sn Alloy: effect of laser point distance. Key Eng Mater2012; 520: 226–233.
9.
GuDDMeinersWWissenbachK, et al.Laser additive manufacturing of metallic components: materials, processes and mechanisms. Int Mater Rev2012; 57: 133–164.
10.
HerzogDSeydaVWyciskE, et al.Additive manufacturing of metals. Acta Mater2016; 117: 371–392.
11.
MurrLEGaytanSMRamirezDA, et al.Metal Fabrication by additive manufacturing using laser and electron beam melting technologies. J Mater Sci Technol2012; 28: 1–14.
12.
KranzJHerzogDEmmelmannC. Design guidelines for laser additive manufacturing of lightweight structures in TiAl6V4. J Laser Appl2015; 27: S14001.
13.
TanXKokYTanYJ, et al.Graded microstructure and mechanical properties of additive manufactured Ti–6Al–4V via electron beam melting. Acta Mater2015; 97: 1–16.
14.
MurrLEEsquivelEVQuinonesSA, et al.Microstructures and mechanical properties of electron beam-rapid manufactured Ti–6Al–4V biomedical prototypes compared to wrought Ti–6Al–4V. Mater Charact2009; 60: 96–105.
15.
SoaresFMSBarbosaDMCoradoHPR, et al.Surface morphology, roughness, and corrosion resistance of dental implants produced by additive manufacturing. J Mater Res Technol2022; 21: 3844–3855.
16.
LavrysSPohrelyukIVeselivskaH, et al.Corrosion behavior of near-alpha titanium alloy fabricated by additive manufacturing. Mater Corros2022; 73: 2063–2070.
17.
BandekhodaMRMosallanejadMHAtapourM, et al.Investigation on the potential of laser and electron beam additively manufactured Ti-6Al-4V components for orthopedic applications. Met Mater Int2024; 30: 114–126.
18.
WangWH. The elastic properties, elastic models and elastic perspectives of metallic glasses. Prog Mater Sci2012; 57: 487–656.
19.
WuXQPengQZhaoJC, et al.Effect of Sn content on the corrosion behavior of Ti-based biomedical amorphous alloys. Int J Electrochem Sci2015; 10: 2045–2054.
20.
InoueA. Stabilization of metallic supercooled liquid and bulk amorphous alloys. Acta Mater2000; 48: 279–306.
21.
HuaNHongXLinL, et al.Mechanical, corrosion, and wear performances of a biocompatible Ti-based glassy alloy. J Non Cryst Solids2020; 543: 120116.
22.
LiensATer-OvanessianBCourtoisN, et al.Effect of alloying elements on the microstructure and corrosion behavior of TiZr-based bulk metallic glasses. Corros Sci2020; 177: 108854.
23.
ZhuSWangXQinF, et al.Glass-forming ability and thermal stability of Ti–Zr–Cu–Pd–Si bulk glassy alloys for biomedical applications. Mater Trans2007; 48: 163–166.
24.
AbdiSOswaldSGostinPF, et al.Designing new biocompatible glass-forming Ti75-xZr10NbxSi15 (x = 0, 15) alloys: corrosion, passivity, and apatite formation. J Biomed Mater Res B2016; 104: 27–38.
25.
FanJZhuSWangXJ. Failure of a Ti-based metallic glass matrix composite upon high-temperature annealing. Met Mater Int2020; 26: 285–291.
QinFWangXZhuS, et al.Fabrication and corrosion property of novel Ti-based bulk glassy alloys without Ni. Mater Trans2007; 48: 515–518.
28.
WangLChuHXieJ, et al.Comparative study on the microbial corrosion resistance of mortars with Cu-Ti amorphous alloys and TiO2 nanoparticles. Constr Build Mater2024; 448: 138200.
29.
BodunrinMOChownLHMerweJW, et al.Corrosion behavior of titanium alloys in acidic and saline media: role of alloy design, passivation integrity, and electrolyte modification. Corros Rev2020; 38: 25–47.
30.
Jáquez-MuñozJMGaona-TiburcioCChacón-NavaJ, et al.Electrochemical corrosion of titanium and titanium alloys anodized in H2SO4 and H3PO4 Solutions. Coatings2022; 12: 325.
31.
LiXWangLFanL, et al.Understanding the effect of fluoride on corrosion behavior of pure titanium in different acids. Corros Sci2021; 192: 109812.
32.
ChenBYanTWangT, et al.Gradient structure formation and corrosion behavior of Ti45.5Zr6.5Cu39.9Ni5.1Sn2Si1 amorphous alloy induced by laser surface melting. J Mater Res Technol2024; 33: 4587–4593.
33.
WangWCuiWXiaoZ, et al.The improved corrosion and wear properties of Ti-Zr based alloys with oxide coating in simulated seawater environment. Surf Coat Tech2022; 439: 128415.
34.
SeoBParkHKParkCS, et al.Role of Ta in improving corrosion resistance of titanium alloys under highly reducing condition. J Mater Res Technol2023; 23: 4955–4964.
35.
AkbarpourMRMirabadHMHemmatiA, et al.Processing and microstructure of Ti-Cu binary alloys: a comprehensive review. Prog Mater Sci2022; 127: 100933.
36.
MaCSoejimaHIshiharaS, et al.New Ti-based bulk glassy alloys with high glass-forming ability and superior mechanical properties. Mater Trans2004; 45: 3223–3227.
37.
ZhangMSongYQLinHJ, et al.A brief introduction on the development of Ti-based metallic glasses. Front Mater2022; 8: 814629.
38.
CaiFFBlanquerACostaMB, et al.Hierarchical surface pattern on Ni-free Ti-based bulk metallic glass to control cell interactions. Small2024; 20: 2310364.
39.
TaylorTPDingMEhlerDS, et al.Beryllium in the environment: a review. J Environ Sci Health A2003; A38: 439–469.
40.
GongPDengLJinJ, et al.Review on the research and development of Ti-based bulk metallic glasses. Metals2016; 6: 264.
41.
YüceEZarazúa-VillalobosLTer-OvanessianB, et al.New-generation biocompatible Ti-based metallic glass ribbons for flexible implants. Mater Des2022; 223: 111139.
42.
ChenFCDaiFPYangXY, et al.Effect of Sn and Al additions on the microstructure and mechanical properties of amorphous Ti–Cu–Zr–Ni alloys. Chin Phys B2020; 29: 066401.
43.
ZhangYJiazhuoLEIZhenhuaDAN, et al.Combinatorial effects of the recipes of the initial gas-atomized powder sizes on microstructure and passivation characteristics of the SLM-ed Ti-6Al-4V bulk alloys. Mater Sci2023; 29: 176–185.
44.
LiXZhangLShiT, et al.Preparation and electrochemical characterization of Ti-based amorphous metallic glass with high strength. Mater Corros2021; 72: 951–959.
45.
PetzoldtFFriedericiVImgrundP, et al.Advanced PM process for medical technologies. J Kor Powd Met Inst2014; 21: 1–6.
46.
DaviesHA. Processing, properties, and applications of rapidly solidified advanced alloy powders. Powder Metall1990; 33: 223–233.
47.
BloyceAQiPYDongH, et al.Surface modification of titanium alloys for combined improvements in corrosion and wear resistance. Surf Coat Tech1998; 107: 125–132.
48.
SeoBParkHKParkCS, et al.Effect of alloying elements on corrosion properties of high corrosion resistant titanium alloys in high concentrated sulfuric acid. Mater Today Commun2023; 34: 105131.
49.
MeiJSoubeyrouxJLBlandinJJ. Structural relaxation of Ti-based bulk metallic glasses. Titane2011: 1–5.
50.
HuangYJShenJSunJF, et al.A new Ti–Zr–Hf–Cu–Ni–Si–Sn bulk amorphous alloy with high glass-forming ability. J Alloy Compd2007; 427: 171–175.
51.
MeiJNSoubeyrouxJLBlandinJJ, et al.Homogeneous deformation of Ti41.5Cu37.5Ni7.5Zr2.5Hf5Sn5Si1 bulk metallic glass in the supercooled liquid region. Intermetallics2011; 19: 48–53.
52.
MaCIshiharaSSoejimaH, et al.Formation of new Ti-based metallic glassy alloys. Mater Trans2004; 45: 1802–1806.
53.
InoueA. High strength bulk amorphous alloys with low critical cooling rates (Overview). Mater Trans, JIM1995; 36: 866–875.
54.
LouzguineDVYavariARInoueA. Mischmetal as an alloying addition to amorphous materials and glass formers. J Non Cryst Solids2003; 316: 255–260.
55.
WuXMengLZhaoW, et al.Crystallization kinetics of misch metal based bulk metallic glasses. J Rare Earth2007; 25: 189–193.
56.
WolfeRCShawBA. The effect of thermal treatment on the corrosion properties of vapor deposited magnesium alloyed with yttrium, aluminum, titanium, and misch metal. J Alloy Compd2007; 437: 157–164.
57.
LiRPangSMaC, et al.Influence of similar atom substitution on glass formation in (La–Ce)–Al–Co bulk metallic glasses. Acta Mater2007; 55: 3719–3726.
58.
HongHNHoangVNPhamQ, et al.Microstructure formation of Al-based alloys in the presence of rare earth metals (Ce, La) and Mn under high cooling rate. J Mater Eng Perform2024: 1–12.
