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Article

Simultaneous Improvement of Glass-Forming Ability and Ductility in Co-Based BMGs Through Si/Fe Microalloying

by
Xinlong Quan
1,
Liming Xu
1,
Yong Zhao
1,*,
Xuecheng Tang
1,
Qing Liu
1,
Bo Zhang
1,* and
Wei-Hua Wang
1,2
1
Songshan Lake Materials Laboratory, Dongguan 523770, China
2
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
*
Authors to whom correspondence should be addressed.
Metals 2025, 15(9), 943; https://doi.org/10.3390/met15090943
Submission received: 10 July 2025 / Revised: 17 August 2025 / Accepted: 22 August 2025 / Published: 25 August 2025
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Abstract

Cobalt-based bulk metallic glasses (Co-based BMGs) offer a combination of high strength, corrosion resistance, and soft magnetic properties, yet their limited glass-forming ability (GFA) and poor room-temperature ductility restrict broader application. In this study, a microalloying strategy was applied to the Co61Nb8B31 base composition to develop Co-Nb-B-Si and Co-Fe-Nb-B-Si systems. The effects of Si addition and Fe substitution on GFA, thermal stability, and mechanical properties were systematically investigated. Si doping combined with Co/B ratio tuning broadened the supercooled liquid region and increased the critical glass-forming diameter from 1 mm to 3 mm. Further addition of 5 at.% Fe expanded the supercooled liquid region and enabled the fabrication of a fully amorphous plate with 1 mm thickness. The optimized Co63Nb8B27Si2 alloy exhibited a compressive strength of 5.18 GPa and a plastic strain of 3.81%. Fracture surface analysis revealed ductile fracture features in the Si-containing alloy and brittle characteristics in Fe-rich compositions. These results demonstrate that microalloying is effective in optimizing the balance between GFA and mechanical performance of Co-based BMGs, offering guidance for composition and processing design.

1. Introduction

Cobalt-based bulk metallic glasses (Co-based BMGs) possess a unique combination of high strength, good corrosion resistance, and favorable soft magnetic properties, making them promising candidates for structurally and functionally integrated applications [1,2,3,4,5,6]. However, their widespread application is severely restricted by two critical limitations: low glass-forming ability (GFA), typically reflected by a critical glass-forming diameter (Dc) of less than 3 mm [7,8,9], and poor room-temperature ductility characterized by brittle fracture [10,11]. Although prior studies have attempted to overcome these limitations, the progress has been largely unbalanced. For example, the Co-Ta-B system exhibits exceptional strength exceeding 5.8 GPa [12], yet remains nearly brittle, showing negligible plastic strain despite GFA improvement through Co/B ratio adjustment. In contrast, the Co-(Fe)-Cr-Mo-C-B-Er system achieves a large Dc of 15 mm but still suffers from catastrophic brittle failure [13]. Meanwhile, the Co-Fe-Nb-B-Si system developed by Shen et al. exhibited slight plasticity (~0.25%) through Fe incorporation and Nb addition, but excessive Fe severely degraded the strength to below 4.5 GPa [14]. These examples highlight a central challenge in Co-based BMG research: how to simultaneously achieve high GFA, high strength, and appreciable plastic deformability, which is critical for enabling reliable and scalable applications.
The GFA of BMG fundamentally relies on suppressing crystallization during rapid cooling, which depends on factors such as atomic size mismatch, chemical interactions, and configurational entropy. Inoue’s empirical rules [15], which emphasize multicomponent systems with large atomic size mismatches and negative mixing enthalpies, have effectively guided the design of BMGs. In Co-based systems, higher GFA has been correlated to broader supercooled liquid regions (ΔTx) [16,17], improved liquid stability [3,18], and denser atomic packing featuring icosahedral-like local structures [19,20,21]. Previous studies [17,22,23] demonstrated that strategies such as metalloid content modulation and similar element substitution are effective in frustrating crystal nucleation by increasing chemical and topological disorder. For example, Zhao et al. [24] developed Co-Ta-B-Si alloys with a critical diameter of up to 4 mm. By partially replacing B with Si and optimizing the Co/B atomic ratio, they achieved a high fracture strength of 5.5 GPa and a plastic strain of 6.4%. Similarly, substituting Fe for Co in the (Co1−yFey)71.5Y3.5B25 series increased the Dc from <1 mm to 2 mm and expanded ΔTx from 33 K to 50 K [7,25]. Molecular dynamics simulations further revealed that such substitution enhance GFA by increasing the fraction of non-distorted clusters [25].
In terms of mechanical behavior, the inherent brittleness of Co-based BMGs originates from highly localized shear banding with limited strain hardening. Achieving ductility requires microstructural heterogeneity that promotes the activation of multiple shear bands and dissipates energy through their interaction [2,26]. Previous studies [27] have shown that compositional tuning, particularly reducing strong covalent bonds (e.g., excessive B-B or B-M) and altering medium-range order, can effectively enhance plastic strain without sacrificing strength.
Within this framework, microalloying—the deliberate introduction of minor alloying elements to tailor bonding and disrupt local structural order—has emerged as a promising strategy to simultaneously enhance GFA and mechanical properties [28,29,30,31]. For example, Si doping can improve atomic packing density and directional bonding, thereby broadening ΔTx [32,33]. Meanwhile, introducing Fe, a chemically analogous element to Co with strong negative mixing enthalpies, increases configurational entropy and frustrates crystallization, potentially improving both processability and toughness [25,34].
In this study, we used a high-strength but low-GFA alloy Co61Nb8B31 [27] as the base composition and applied a microalloying strategy to design a series of Co-Nb-B-Si and Co-Fe-Nb-B-Si BMGs. By adjusting the Co/B ratio, substituting B with Si, and introducing minor amounts of Fe in place of Co, we systematically investigated the effects of compositional tuning on the GFA, thermal stability, and mechanical properties. The optimized composition Co63Nb8B27Si2 exhibits a critical diameter of 3 mm, a plastic strain of 3.81%, and a compressive strength exceeding 5.1 GPa, representing a balanced advancement in both formability and mechanical performance. The fracture morphology further confirms the enhanced structural stability and ductile behavior induced by this microalloying approach.

2. Materials and Methods

Alloy ingots with nominal compositions of Co61+xNb8B29−xSi2 (x = 0–5) and Co63−yFeyNb8B27Si2 (y = 3–7) in atomic percent were prepared by arc-melting high-purity raw elements—Co (99.999 wt.%), Nb (99.95 wt.%), B (99.99 wt.%), Si (99.99 wt.%), and Fe (99.99 wt.%)—in a high-purity argon atmosphere. To ensure chemical homogeneity, each ingot was remelted at least five times before being suction-cast into copper molds to form cylindrical rods of various diameters. The amorphous structures of the as-cast samples were characterized by X-ray diffraction (XRD, MiniFlex600-C, Rigaku Corporation, Tokyo, Japan). Thermal properties were measured using differential scanning calorimetry (DSC, Netzsch 404 F3, Netzsch-Gerätebau GmbH, Selb, Germany) at a constant heating rate of 20 K/min. Mechanical properties were evaluated through uniaxial compression tests using a universal testing machine (MTS CMT5504, MTS Systems Corporation, Eden Prairie, MN, USA). Cylindrical specimens with a diameter of 1 mm and a height of 2 mm were tested at a strain rate of 1 × 10−4 s−1 to obtain compressive strength and plastic strain. Fracture morphologies of the deformed samples were examined by field-emission scanning electron microscopy (FE-SEM, TESCAN, Brno, Czech Republic) for comparative analysis of deformation modes.

3. Results and Discussion

3.1. Composition Design of Co-Based BMGs with Enhanced GFA

To improve the limited GFA of the high-strength Co61Nb8B31 alloy, compositional tuning was conducted by introducing minor alloying elements. Two main strategies were employed: (1) partially substituting B with Si to adjust the Co/B ratio and metalloid content, and (2) replacing Co with Fe to enhance configurational entropy and frustrate crystallization.
Figure 1a shows the XRD patterns of as-cast Co61+xNb8B29−xSi2 (x = 0–5) alloy rods with diameters ranging from 1 to 4 mm. Dc increases from 1 mm for the base composition to 3 mm at x = 2, confirming that moderate Si substitution and Co/B ratio tuning effectively enhance GFA. This improvement is likely due to reduced directional bonding, suppressed nucleation, and to the more flexible local coordination environments introduced by Si.
Additionally, as observed in Figure 1a, variations in B concentration lead to changes in the crystallization phases of the Co61+xNb8B29−xSi2 (x = 0–5) alloys. The x = 0 alloy crystallizes into Co2B and Co13B7. The x = 2 alloy, for which the 4 mm diameter sample was examined, also shows Co2B and Co13B7 as the main crystalline phases. At x = 5, the dominant phase shifts to Co2Nb. Peak analysis confirms that Co2B and Co13B7 are commonly observed metastable phases in Co-based amorphous alloys upon devitrification [12]. The appearance of Co2Nb at high Co/B ratios (e.g., x = 5) likely results from B deficiency, which favors the formation of the more thermodynamically stable Co-Nb binary intermetallic phase when insufficient B remains to form Co-B compounds. This behavior is consistent with the understanding that metalloid content, especially that of B, plays critical roles in glass stability and crystallization pathways [24,35].
To further investigate the effect of chemical complexity on glass formation, Fe was partially substituted for Co in the optimized Co63Nb8B27Si2 alloy. Based on the criterion of negative mixing enthalpy [36], Fe exhibits strong chemical affinity with other constituent elements in the system, including Co (−1 kJ/mol), Nb (−16 kJ/mol), B (−26 kJ/mol), and Si (−35 kJ/mol), making it a promising candidate for similar-element substitution, as shown in Figure 1b. Accordingly, a second alloy series, Co63−yFeyNb8B27Si2 (y = 3–7), was designed to systematically evaluate the effect of Fe addition on the GFA and processability of the Co-based system.
Figure 1c,d present the XRD patterns of Co63−yFeyNb8B27Si2 (y = 3–7) rod samples to determine Dc and reflect the GFA variation. As observed in Figure 1c, the addition of Fe maintains the critical diameter at 3 mm, failing to produce amorphous alloys with a diameter of 4 mm. However, Figure 1d demonstrates that with Fe addition, a plate-shaped sample (1 mm thick, 10 mm wide, and 50 mm long) of Co58Fe5Nb8B27Si2 can be successfully fabricated, exhibiting a fully amorphous XRD pattern, whereas the Fe-free counterpart (Co63Nb8B27Si2) shows crystallization peaks under identical casting conditions. This contrast demonstrates that Fe addition enables glass formation in larger and more geometrically complex castings, likely due to increased configurational entropy and disruption of crystalline ordering pathways, consistent with the “confusion principle” [22].
We further investigated the crystallization phases in the Co63−yFeyNb8B27Si2 (y = 3–7) alloys. As shown in Figure 1c, the y = 3 alloy contains (Co, Fe)23B6 as the dominant crystalline phase; with y = 5, both (Co, Fe)23B6 and Fe2B are present; and with y = 7, Fe2B and Fe2Si become the main crystalline products. Peak-fitting analysis indicates that (Co, Fe)23B6 is a complex boride phase frequently reported in Co-Fe-based BMGs during devitrification [37,38]. At higher Fe levels, the increased availability of Fe promotes the formation of Fe-B-type compounds and Fe-Si phases, depending on the local chemical environment and atomic diffusion kinetics during cooling. The presence of Si also influences the crystallization pathway, though to a lesser extent than Fe and B; Si can form Fe-Si or Co-Si compounds in later stages of devitrification, particularly when metalloid depletion (B loss) leads to a compositional imbalance, as reflected in the emergence of Fe2Si at high Fe contents.

3.2. Thermal Properties

Figure 2a,b show the DSC curves of Co61+xNb8B29−xSi2 (x = 0–5) alloys at a heating rate of 20 K/min, covering both the glass transition and melting regions. For x = 0 to 4, clear glass transition events followed by exothermic crystallization peaks are observed, indicating the existence of the supercooled liquid region. In contrast, for x = 5, the absence of an evident endothermic glass transition and the dominance of sharp crystallization peaks suggest partial crystallization during casting. The glass transition temperature (Tg) of this alloy series lies in the range of 872.9 K–899.3 K, and the ΔTx spans from 33.7 K to 44.5 K, reflecting favorable thermal stability. With increasing Co/B ratio (i.e., decreasing B content), a gradual decline in Tg is observed, which can be attributed to the reduction in high-melting-point B and the corresponding weakening of network rigidity. The optimized composition Co63Nb8B27Si2 (x = 2) exhibits a broad supercooled liquid region of 38.6 K, correlating well with its enhanced GFA.
A pronounced reduction in crystallization temperature (Tx) of the alloys can be observed with increasing Co content, which could be explained by two factors: (i) a shift in bonding from strong covalent B-M (M = Nb, Co) to more metallic Co-Co and Co-Si interactions, reducing the network rigidity and facilitating atomic rearrangement [2,7,24]; and (ii) diminished thermodynamic stability of the amorphous phase as the strongly negative mixing enthalpies between B and Co/Nb are reduced, weakening the chemical driving force for glass formation. Consequently, both Tx and Tg decrease with higher Co/B ratios, consistent with previous reports [24,39].
A progressive increase in the melting temperature (Tm) was observed with rising Co/B ratio; particularly, when the ratio increased from x = 2 to x = 3, Tm increased from 1387 K to 1410 K. The marked change in melting behavior, particularly the increase in Tm, could be explained from two perspectives. First, increasing Co content (and thus reducing B content) shifts the alloy composition into a region of higher-melting-point intermetallic compounds. XRD phase analysis shows that alloys with lower Co/B ratios tend to form quasi-eutectic Co-B phases (e.g., Co2B, Co13B7), whereas with higher Co/B ratios (x > 2), the primary crystalline phase changes to Co2Nb, which has a substantially higher melting point [40,41]. Second, the suppression of eutectic-like behavior also contributes to the temperature increase. At low x values (e.g., x = 1–2), higher B content promotes Co-B-type amorphous phases often associated with pseudo-eutectic compositions, which exhibit a depressed liquidus temperature and thus a lower apparent melting point. When B content decreases (x ≥ 4), this eutectic-like effect is lost, and the system shifts toward a more ordered and thermodynamically stable crystalline regime, sharply elevating the melting temperature [42,43]. Such a pronounced change with only minor variation in the Co/B ratio is typical for compositions located near eutectic or phase-boundary regions, where even small compositional shifts can abruptly alter the dominant crystalline phases and liquidus temperature.
Figure 2c,d present the thermal response of Co63−yFeyNb8B27Si2 (y = 3–7) alloys. As Fe content increases from 0 to 5, the supercooled liquid region broadens from 38.6 K to 44.2 K at y = 5. The enlarged ΔTx suggests improved stability of the undercooled liquid, where atomic rearrangement is kinetically hindered, facilitating the retention of disordered structures upon cooling [44]. The thermodynamic parameters, including Tg, Tx, Tm, liquidus temperature (Tl), and ΔTx, for both the Co-Nb-B-Si and Co-Fe-Nb-B-Si BMG series are summarized in Table 1.
A non-monotonic trend in the Tx with increasing Fe content (an initial decrease followed by a subsequent increase) can be observed as a slight decrease from y = 3 to y = 5, followed by an increase at y > 5, which could originate from the competition between structural destabilization and chemical stabilization effects introduced by Fe substitution. At low Fe contents (y = 3–5), Fe substitution for Co is expected to perturb Co-centered atomic clusters and disrupt the short-range order of the amorphous matrix. Although Co and Fe have similar atomic radii, their different electronegativities and bonding preferences lower the activation energy for atomic rearrangement, promoting earlier crystallization and slightly reducing Tx. Similar initial decreases in Tx have been reported in other Co-Fe-B-Si systems, where the minimum Tx often appears near compositions with optimal GFA [17]. When the Fe content exceeds y = 5, stabilizing effects outweigh the initial destabilization. First, Fe–B bonds have a more negative mixing enthalpy (−26 kJ/mol) than Co-B bonds do (−24 kJ/mol), strengthening chemical bonding and enhancing the thermodynamic stability of the undercooled liquid [30,39]. Second, higher Fe content increases chemical complexity, which raises configurational entropy and frustrates crystallization in accordance with the “confusion principle” [29]. Together, these factors delay the onset of crystallization, resulting in a rebound of Tx at higher Fe contents.

3.3. Mechanical Properties

The mechanical performance of the optimized alloys was evaluated via uniaxial compression tests. Figure 3 displays the stress–strain curves of selected Co-Nb-B-Si and Co-Fe-Nb-B-Si BMGs. Among them, the Co63Nb8B27Si2 composition exhibits the best strength–plasticity balance, with a compressive fracture strength of 5.18 GPa and a plastic strain of 3.81%. This composition achieves the best combination of GFA (Dc = 3 mm) and ductility. The improvement is consistent with self-organized criticality behavior [45], where enhanced shear-band multiplication and branching promote stable plastic flow, as also reported in BMGs with optimized metalloid contents [24]. In contrast, excessive B reduction (x ≥ 4) degrades network connectivity, suppresses shear-band branching, and leads to embrittlement and reduced strength, consistent with prior studies [10,24]. Upon partial substitution of Co with Fe (y = 3), the resulting Co60Fe3Nb8B27Si2 alloy maintains high mechanical performance, achieving 5.01 GPa in strength and 2.86% in plastic strain. Increasing Fe to y = 4–5 causes a progressive drop in both strength and plasticity, with plasticity falling below 1% at y = 5. At y ≥ 6, alloys fail in a brittle manner and display low strength and negligible plastic strain. Moderate Fe addition likely increases chemical disorder and preserves a ductile amorphous structure, whereas excessive Fe leads to over-homogenization of the bonding environment, reducing shear-band multiplication and promoting localized deformation, ultimately causing early fracture [23]. Even so, the Co58Fe5Nb8B27Si2 alloy still exhibits 4.63 GPa in strength and moderate deformability (0.85%), which is superior to many previously reported Fe-rich BMGs [14,46,47,48,49].
Overall, compositional tuning can enhance both GFA and plasticity, particularly in the Co63Nb8B27Si2 and Co60Fe3Nb8B27Si2 alloys. The strength–plasticity trade-off is highly sensitive to small alloying changes, especially those in B and Fe content. The stress–strain curves clearly illustrate the transition from ductile to brittle fracture. These results support the use of microalloying strategies to control shear-band behavior and optimize the mechanical reliability of Co-based BMGs.
The elastic modulus was determined by fitting the elastic deformation region of the stress–strain curves in Figure 3. As presented in Table 1, the addition of Si increased the elastic modulus (E) from 225 GPa to 239 GPa. Subsequently, as the Co content or Co/B ratio increases, the modulus exhibits a decreasing trend, reaching 228 GPa and 222 GPa for the Co63Nb8B27Si2 and Co66Nb8B24Si2 alloys, respectively. Furthermore, Fe substitution for Co generally enhanced the modulus, reaching a maximum value of 246 GPa for the Co56Fe7Nb8B27Si2 alloy. Small amounts of Si (a metalloid that forms relatively stiff local bonds and promotes denser local packing) increase the bond-energy density of the glassy network and therefore raise the modulus [50]. As the Co/B ratio rises, the proportion of stiff covalent B-M (M = Co, Nb) bonds decreases relative to more metallic Co-Co bonding, resulting in reduced average bond stiffness and a lower modulus [12]. Substituting Co with Fe raises the modulus at high Fe content, which could be attributed to Fe-B bonds having a more negative mixing enthalpy (−26 kJ/mol) than Co-B bonds do (−24 kJ/mol), thereby strengthening chemical bonding and toughening the matrix [39].
A broader comparison of mechanical performance is presented in Figure 4, which plots fracture strength (σf) versus plastic strain (εp) for various Co-based BMGs [2,9,12,13,17,24,51,52,53,54,55]. Alloys developed in this work are located in the upper-right region of the plot—representing a favorable combination of high strength, appreciable ductility, and Dc (indicated by marker size). Their positions in the performance map demonstrate that the present alloys effectively overcome the conventional strength–plasticity trade-off and exhibit improved castability, making them promising candidates for structural–functional applications.
The GFA of the Co-Nb-B-Si system is fundamentally governed by compositional tuning, which modifies both thermodynamic stability and atomic packing frustration. As shown by the DSC results and critical casting diameter data (Figure 2 and Table 1), Si addition slightly reduces Tg but significantly raises the Tx, leading to a markedly enlarged ΔTx. Further adjustment of the Co/B ratio results in a concurrent decrease in both Tg and Tx, while ΔTx first increases and then decreases, reaching a maximum at an optimal ratio (x = 1–3), where the Dc is also maximized. This enhancement is attributed to the synergistic effect of Si addition and Co/B ratio tuning, which reduces the population of tightly bonded B–B and Nb-B clusters. These structural modifications weaken directional bonding, increase topological disorder and configurational entropy, and suppress crystallization during cooling, thereby improving GFA [24]. Further incorporation of Fe (y = 3–7) into the optimized Co63Nb8B27Si2 composition introduces additional chemical complexity without significantly altering atomic size, as Fe and Co have nearly identical radii. However, Fe exhibits more negative mixing enthalpies with B and Nb (−26 and −16 kJ/mol, respectively), and its addition increases the entropy of mixing, thus further stabilizing the supercooled liquid. This effect is evidenced by the broader ΔTx observed in Fe-containing alloys, reaching up to 44.2 K at y = 5, indicating enhanced kinetic resistance to crystallization.
The variation in mechanical properties among the developed alloys is closely connected to their microscopic deformation mechanisms, as revealed by the fracture surface morphologies shown in Figure 5. The Co63Nb8B27Si2 alloy (Figure 5a,b) displays clear signatures of ductile fracture, including multiple deep dimples and branching shear bands. These features reflect extensive localized plastic flow and effective energy dissipation. The presence of such ductile characteristics is attributed to a structurally heterogeneous amorphous matrix, where varied atomic bonding environments facilitate shear-band multiplication and delay catastrophic failure [45]. In contrast, the Fe-containing Co58Fe5Nb8B27Si2 alloy (Figure 5c,d) exhibits a dominant radial main shear band with minimal secondary bifurcation and smooth, mirror-like fracture zones—hallmarks of brittle failure. This behavior suggests a more homogeneous glassy structure where deformation is highly localized. Moreover, the partial loss of bonding heterogeneity due to excessive Fe substitution likely weakens the alloy’s ability to nucleate and deflect shear bands, leading to premature failure. Although vein patterns are observed in limited regions (Figure 5d), their localized nature and instability under high stress hinder the development of substantial plasticity.

4. Conclusions

In this work, a series of Co-Nb-B-Si and Fe-substituted Co-Fe-Nb-B-Si bulk metallic glasses were systematically developed and investigated. By optimizing the Co/B ratio and introducing minor Fe additions, the alloys exhibited enhanced GFA, thermal stability, and mechanical performance. The improvement in GFA is attributed to favorable atomic size mismatch, negative mixing enthalpy, and increased configurational entropy, which jointly suppress crystallization. Furthermore, the alloy with optimal composition shows a high compressive strength and distinct plasticity, as revealed by stress–strain behavior and fracture morphology. These findings provide valuable insights into the compositional tuning strategies for designing high-performance Co-based bulk metallic glasses.

Author Contributions

Conceptualization, Y.Z., B.Z. and W.-H.W.; methodology, Y.Z. and X.Q.; validation, X.Q., L.X., Q.L. and X.T.; formal analysis, Y.Z. and X.Q.; investigation, X.Q., L.X., Q.L. and X.T.; resources, B.Z. and W.-H.W.; data curation, X.Q., L.X., Q.L. and X.T.; writing—original draft preparation, X.Q., Y.Z. and B.Z.; writing—review and editing, X.Q., Y.Z., B.Z. and W.-H.W.; supervision, Y.Z., B.Z. and W.-H.W.; project administration, B.Z. and W.-H.W.; funding acquisition, B.Z. and W.-H.W. All authors have read and agreed to the published version of the manuscript.

Funding

The work was financially supported by the National Key Research and Development Program of China (No. 2021YFA0716302), the National Natural Science Foundation of China (Nos. 52325104 and 52101199), the Guangdong Basic and Applied Basic Research Foundation, China (No. 2022A1515140115), and Songshan Lake Materials Laboratory (No. SLZL01-03). Y. Zhao acknowledges the financial support of the Songhu Youth Scholar Program from the Songshan Lake Materials Laboratory.

Data Availability Statement

The original contributions presented in this study are included in the article. Further inquiries can be directed to the corresponding authors.

Conflicts of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Metals 15 00943 g001
Figure 1. (a) XRD patterns of the as-cast Co61+xNb8B29−xSi2 (x = 0–5) BMGs with Dc; (b) schematic diagram showing the mixing enthalpies between Co, Nb, B, Si, and Fe; (c) XRD patterns of the as-cast Co63−yFeyNb8B27Si2 (y = 3–7) alloy rods; and (d) XRD patterns of the plate samples of Co63Nb8B27Si2 and Co58Fe5Nb8B27Si2 with 1 mm thickness.
Figure 1. (a) XRD patterns of the as-cast Co61+xNb8B29−xSi2 (x = 0–5) BMGs with Dc; (b) schematic diagram showing the mixing enthalpies between Co, Nb, B, Si, and Fe; (c) XRD patterns of the as-cast Co63−yFeyNb8B27Si2 (y = 3–7) alloy rods; and (d) XRD patterns of the plate samples of Co63Nb8B27Si2 and Co58Fe5Nb8B27Si2 with 1 mm thickness.
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Figure 2. DSC curves of Co-based BMGs recorded at a heating rate of 20 K/min: (a) glass transition and crystallization and (b) melting behaviors of Co61+xNb8B29−xSi2 (x = 0–5) alloys; (c) glass transition and crystallization and (d) melting behaviors of Co63−yFeyNb8B27Si2 (y = 3–7) alloys. Arrows denote the characteristic temperatures (Tg, Tx, Tm, and Tl ), determined from the intersections of the tangents to the DSC curves.
Figure 2. DSC curves of Co-based BMGs recorded at a heating rate of 20 K/min: (a) glass transition and crystallization and (b) melting behaviors of Co61+xNb8B29−xSi2 (x = 0–5) alloys; (c) glass transition and crystallization and (d) melting behaviors of Co63−yFeyNb8B27Si2 (y = 3–7) alloys. Arrows denote the characteristic temperatures (Tg, Tx, Tm, and Tl ), determined from the intersections of the tangents to the DSC curves.
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Figure 3. Compressive stress–strain curves of Co61+xNb8B29−xSi2 (x = 0–5) and Co63−yFeyNb8B27Si2 (y = 3–7) BMGs under uniaxial compression.
Figure 3. Compressive stress–strain curves of Co61+xNb8B29−xSi2 (x = 0–5) and Co63−yFeyNb8B27Si2 (y = 3–7) BMGs under uniaxial compression.
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Figure 4. Fracture strength (σf) and plastic strain (εp) for the present Co-Nb-B-Si and Co-Fe-Nb-B-Si BMGs and other representative Co-based BMGs reported in the literature [2,9,12,13,17,24,51,52,53,54,55]. Each data point represents a specific composition, with the marker size corresponding to the Dc of the alloy. The present alloys, marked in red and purple, exhibit a favorable balance between strength, ductility, and GFA, as evidenced by their location in the upper-right region of the performance map.
Figure 4. Fracture strength (σf) and plastic strain (εp) for the present Co-Nb-B-Si and Co-Fe-Nb-B-Si BMGs and other representative Co-based BMGs reported in the literature [2,9,12,13,17,24,51,52,53,54,55]. Each data point represents a specific composition, with the marker size corresponding to the Dc of the alloy. The present alloys, marked in red and purple, exhibit a favorable balance between strength, ductility, and GFA, as evidenced by their location in the upper-right region of the performance map.
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Figure 5. SEM images of fracture surface morphologies of (a,b) Co63Nb8B27Si2 and (c,d) Co58Fe5Nb8B27Si2 alloys at different magnifications. Images (a,b) show dimpled features and shear-band branching at low and high magnifications, characteristic of ductile fracture. Images (c,d) reveal a dominant shear band and smooth fracture surfaces with limited vein patterns, indicating a more localized and brittle failure mode.
Figure 5. SEM images of fracture surface morphologies of (a,b) Co63Nb8B27Si2 and (c,d) Co58Fe5Nb8B27Si2 alloys at different magnifications. Images (a,b) show dimpled features and shear-band branching at low and high magnifications, characteristic of ductile fracture. Images (c,d) reveal a dominant shear band and smooth fracture surfaces with limited vein patterns, indicating a more localized and brittle failure mode.
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Table 1. Dc, thermodynamic parameters (Tg, Tx, Tm, Tl, and ΔTx), and mechanical properties (fracture strength σf, plastic strain εp, and elastic modulus E) of Co61+xNb8B29−xSi2 (x = 0–5) and Co63−yFeyNb8B27Si2 (y = 3–7) BMGs. For alloys where no Tg or ΔTx are detected, this is indicated by a hyphen in the table.
Table 1. Dc, thermodynamic parameters (Tg, Tx, Tm, Tl, and ΔTx), and mechanical properties (fracture strength σf, plastic strain εp, and elastic modulus E) of Co61+xNb8B29−xSi2 (x = 0–5) and Co63−yFeyNb8B27Si2 (y = 3–7) BMGs. For alloys where no Tg or ΔTx are detected, this is indicated by a hyphen in the table.
AlloysDc
(mm)		Tg
(K)		Tx
(K)		Tm
(K)		Tl
(K)		ΔTx
(K)		σf
(MPa)		εp
(%)		E
(GPa)
Co61Nb8B311899.6930.71432.51462.131.155761.85225
Co61Nb8B29Si21899.3943.81385.81431.344.554260.68239
Co62Nb8B28Si22891.4929.21384.41431.837.855491.04232
Co63Nb8B27Si23881.0919.61387.41446.838.651773.81228
Co64Nb8B26Si22875.3909.81410.01454.634.543260.29226
Co65Nb8B25Si21872.9906.61422.71465.533.735170.32223
Co66Nb8B24Si2<1-909.71436.51469.9-38710.20222
Co60Fe3Nb8B27Si21881.9927.11383.71440.345.250102.86233
Co59Fe4Nb8B27Si21876.6920.51391.21426.243.947891.11226
Co58Fe5Nb8B27Si23868.5912.71397.01428.844.246280.85236
Co57Fe6Nb8B27Si22879.6921.71393.21427.142.145370.88236
Co56Fe7Nb8B27Si21872.1919.81395.91425.847.744620.77246
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MDPI and ACS Style

Quan, X.; Xu, L.; Zhao, Y.; Tang, X.; Liu, Q.; Zhang, B.; Wang, W.-H. Simultaneous Improvement of Glass-Forming Ability and Ductility in Co-Based BMGs Through Si/Fe Microalloying. Metals 2025, 15, 943. https://doi.org/10.3390/met15090943

AMA Style

Quan X, Xu L, Zhao Y, Tang X, Liu Q, Zhang B, Wang W-H. Simultaneous Improvement of Glass-Forming Ability and Ductility in Co-Based BMGs Through Si/Fe Microalloying. Metals. 2025; 15(9):943. https://doi.org/10.3390/met15090943

Chicago/Turabian Style

Quan, Xinlong, Liming Xu, Yong Zhao, Xuecheng Tang, Qing Liu, Bo Zhang, and Wei-Hua Wang. 2025. "Simultaneous Improvement of Glass-Forming Ability and Ductility in Co-Based BMGs Through Si/Fe Microalloying" Metals 15, no. 9: 943. https://doi.org/10.3390/met15090943

APA Style

Quan, X., Xu, L., Zhao, Y., Tang, X., Liu, Q., Zhang, B., & Wang, W.-H. (2025). Simultaneous Improvement of Glass-Forming Ability and Ductility in Co-Based BMGs Through Si/Fe Microalloying. Metals, 15(9), 943. https://doi.org/10.3390/met15090943

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