Glass Ribbons Research Articles

Improving the surface characteristics of metallic glass thin ribbons by laser gas nitriding

The single-roll cooling method excels in producing metallic glass ribbons (MGRs), offering rapid cooling rates and exceptional thickness consistency. Nevertheless, a large number of defects including micro-pits and micro-gaps usually appear on the surface of MGRs after the roll forming process, significantly impacting their service life and performance. Laser gas nitriding is a cutting-edge surface modification technology that has been extensively used to improve the comprehensive performance of various metal components. Herein, an attempt was made to simultaneously improve the surface quality and mechanical properties of Zr41.2Ti13.8Cu12.5Ni10Be22.5 MGRs by nanosecond pulsed laser irradiation in a flowing nitrogen atmosphere. The effects of laser irradiation parameters on the surface characteristics of the laser gas nitrided regions were systematically investigated. The experimental results showed that the surface quality of MGRs after laser gas nitriding was enhanced, accompanied by a simultaneous improvement in hardness and scratch resistance. This study underscores laser gas nitriding as a potent strategy to augment the comprehensive surface characteristics of MGRs. This enhancement is poised to significantly extend their service life and reinforce their reliability when utilized as structural and functional materials in sectors such as machinery, national defense, and aerospace.

Self-oxidized AgCu nano-foam with unique phase structure for ethanol sensors breaking through the trade-off between sensitivity and upper linear limit

Comparing to gas ethanol sensors, electrochemical ethanol sensors are promising owing to the low operating temperature, high sensitivity and good accuracy. Common electrochemical ethanol sensors suffer from a general trade-off relationship between sensitivity and upper limit for linear detection. In this work, facile self-oxidized AgCu nano-foam is obtained by simply dealloying of Mg65Ag12.5Cu12.5Y10 metallic glass ribbon in citric acid, which breaks through the trade-off by showing an ultra-high upper linear limit of 1.5 M and good sensitivity of 109.6 μA mM-1 cm-2. Combined experiment and simulation investigations confirm that the ligaments of the AgCu nano-foam is composed of surfaces with interlacing Ag and Cu2O grains that are driven by surface energy, and cores consist of Ag and Cu grains that result from phase separation. Such phase structures, coupled with the geometry merits, lead to fast oxidation dynamics, abundant electroactive sites, good reversibility and stable microstructure, which results in high upper linear limit and a sensitivity improvement of ∼30 times comparing to Cu nano-foam. This work develops a candidate material for high performance sensing of concentrated ethanol, and verifies a promising strategy to prepare efficient catalysts by multilevel-design of geometry and phase structure.

Resistance Spot Welding of Stainless Steel and Titanium Plates with a Supercooled Liquid of Zr55Al10Ni5Cu30 Metallic Glass Ribbons

Resistance Spot Welding of Stainless Steel and Titanium Plates with a Supercooled Liquid of Zr55Al10Ni5Cu30 Metallic Glass Ribbons

Relief transformation of Ni-based metallic glass ribbon upon annealing in β-relaxation region

Relief transformation of Ni-based metallic glass ribbon upon annealing in β-relaxation region

Peracetic acid-induced nanoengineering of Fe-based metallic glass ribbon in application of efficient drinking water treatment

This study presents a novel approach utilizing Fe-Si-B metallic glass-based advanced oxidation processes (AOPs) with peracetic acid (PAA) exposure to mitigate disinfection by-products (DBPs) formation in drinking water treatment. Under optimal conditions, it achieved a 98.21% removal of natural organic matter (NOM) and an 80.64% reduction in DBPs formation. The efficacy is attributed to the galvanic cell effect induced by nanoflower structures on the ribbon surface, produced via PAA exposure, thereby enhancing degradation efficiency. High-valent iron Fe(IV) was identified as the primary reactive species, showing robust cycling efficiency under near-neutral conditions. Continuous flow experiments and toxicity assessments using luminescent bacteria further validated the method, demonstrating minimal metal leaching (<0.146 mg/L) and reduced biotoxicity with a 37.68% inhibition rate decrease in 24 h. These findings underscore the promising potential of PAA-integrated Fe-based amorphous alloys for comprehensive water disinfection and purification.

Mechanical Response of Zr51.9Cu23.3Ni10.5Al14.3 Metallic Glass Ribbon under Varying Strain Rates

In this work, we investigated the mechanical behavior of a low-cost Zr51.9Cu23.3Ni10.5Al14.3 (at. %) metallic glass ribbon prepared with industrial-grade material through the melt-spinning method. The ribbons have good appearances and almost no defects. The mechanical behavior associated with the corresponding microstructure of the ribbon was tested at different strain rates. Striation and veining patterns were observed in the crack propagation zone and the fast fracture zone. The results show that the tensile strength of the ribbons exceeds 1 GPa. Therefore, they are considered to have good potential for industrial applications. This study could contribute to the preparation of low-cost bulk metallic glass.

Anticorrosion and Antimicrobial Tannic Acid-Functionalized Ti-Metallic Glass Ribbons for Dental Abutment.

In this study, a recently reported Ti-based metallic glass (MG), without any toxic element, but with a significant amount of metalloid (Si-Ge-B, 18 atom %) and minor soft element (Sn, 2 atom %), was produced in ribbon form using conventional single-roller melt-spinning. The produced Ti60Zr20Si8Ge7B3Sn2 ribbons were investigated by differential scanning calorimetry and X-ray diffraction to confirm their amorphous structure, and their corrosion properties were further investigated by open-circuit potential and cyclic polarization tests. The ribbon's surface was functionalized by tannic acid, a natural plant-based polyphenol, to enhance its performance in terms of corrosion prevention and antimicrobial efficacy. These properties can potentially be exploited in the premucosal parts of dental implants (abutments). The Folin and Ciocalteu test was used for the quantification of tannic acid (TA) grafted on the ribbon surface and of its redox activity. Fluorescent microscopy and ζ-potential measurements were used to confirm the presence of TA on the surfaces of the ribbons. The cytocompatibility evaluation (indirect and direct) of TA-functionalized Ti60Zr20Si8Ge7B3Sn2 MG ribbons toward primary human gingival fibroblast demonstrated that no significant differences in cell viability were detected between the functionalized and as-produced (control) MG ribbons. Finally, the antibacterial investigation of TA-functionalized samples against Staphylococcus aureus demonstrated the specimens' antimicrobial properties, shown by scanning electron microscopy images after 24 h, presenting a few single colonies remaining on their surfaces. The thickness of bacterial aggregations (biofilm-like) that were formed on the surface of the as-produced samples reduced from 3.5 to 1.5 μm.

Effects of rare-earth element Y content on the microstructure and properties of quinary Al–Ni–Zr–Co–Y high entropy metallic glasses

A series of quinary (Al1/4Ni1/4Zr1/4Co1/4)100-xYx (x = 16–28 at.%) high entropy metallic glass ribbons were successfully fabricated through the high-speed single roller melt-spinning method. The effects of rare-earth element yttrium content on the microstructure and performances of alloy ribbons were systematically investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), heat treatment, transmission electronic microscopy (TEM), atomic force microscopy (AFM) and electrochemical experiments. The microhardness of metallic ribbons was measured by Vickers hardness tester. Results show that the microstructure of the as-quenched alloy ribbons maintain the glassy state and the average microhardness value of each specimen can reach 488 HV0.1 or above. The surface morphologies of the as-spun ribbon samples exhibit the smooth surface with small roughness value of Ra = 0.115–0.150 nm. In the meantime, with the increase of Y content, the glass transition temperature can be detected in the DSC traces when Y content is over 22 at.%, and the crystallization onset temperature shifts to the lower temperature region, suggesting that the thermal stability of amorphous state in Al–Ni–Zr–Co–Y alloy ribbons has been weakened. The (Al1/4Ni1/4Zr1/4Co1/4)84Y16 alloy ribbons own the highest crystallization onset temperature (∼742 K). Adding appropriate yttrium element can enlarge the super-cooled liquid region and improve the glass-forming ability. In 3.5 wt% NaCl solution, the prepared alloy ribbons can maintain smaller corrosion current densities (∼10−8 A cm−2) than traditional Al-based amorphous alloys, 6061 Al alloy and other common structural steels. The X-ray photoelectron spectrometer results indicate that the passive film of equiatomic alloy ribbons is rich in oxides of Al, Zr, Co, and Y elements, which has excellent resistance to chloride ion attack. On the basis of all experimental results, (Al1/4Ni1/4Zr1/4Co1/4)84Y16 alloy ribbons can optimally combine outstanding corrosion resistance, superior thermal stability, and acceptable microhardness. The above research results lay a solid foundation for the composition development of high-performance high entropy metallic glasses.

Excellent magnetocaloric effect near 282 K of a Fe87Ce6Pr4B3 metallic glass ribbon

We reported the excellent magnetocaloric effect near 282 K of a Fe87Ce6Pr4B3 metallic glass in this paper. The Fe87Ce6Pr4B3 metallic glass (MG) was fabricated into the shape of ribbon with typical amorphous characteristics in its X-ray diffraction pattern and differential scanning calorimetry curve. The MG is soft magnetic at 200 K (far below its Curie temperature (Tc ∼ 282 K)) and paramagnetic at 380 K (well above its Tc). The Fe87Ce6Pr4B3 glassy ribbon shows rather high peak of magnetic entropy change (−ΔSmpeak ≈ 3.95 J/(kg × K)) near 282 K under 5 T, which is the highest amongst the Fe-based MGs with Tc around 282 K. The high −ΔSmpeak near 282 K enables it to be employed for the construction of several amorphous hybrids that present flattened −ΔSm profile. The high average −ΔSm from ∼ 282 K to ∼ 315 K of the amorphous hybrids make them better candidates for the high-efficiency refrigerants of the household magnetic air-conditioner.

Constructing Nanoporous Ir/Ta2 O5 Interfaces on Metallic Glass for Durable Acidic Water Oxidation.

Although proton exchange membrane water electrolyzers (PEMWE) are considered as a promising technique for green hydrogen production, it remains crucial to develop intrinsically effective oxygen evolution reaction (OER) electrocatalysts with high activity and durability. Here, a flexible self-supporting electrode with nanoporous Ir/Ta2O5 electroactive surfaceis reported for acidic OER via dealloying IrTaCoB metallic glass ribbons. The catalyst exhibits excellent electrocatalytic OER performance with an overpotential of 218mV for a current density of 10mA cm-2 and a small Tafel slope of 46.1mV dec-1 in acidic media, superior to most electrocatalysts. More impressively, the assembled PEMWE with nanoporous Ir/Ta2 O5 as an anode shows exceptional performance of electrocatalytic hydrogen production and can operate steadily for 260h at 100mA cm-2 . In situ spectroscopy characterizations and density functional theory calculations reveal that the modest adsorption of OOH* intermediates to active Ir sites lower the OER energy barrier, while the electron donation behavior of Ta2 O5 to stabilize the high-valence states of Ir during the OER process extended catalyst's durability.

Flexible multi-layered porous CuxO/NiO (x = 1, 2) photo-assisted electrodes for hybrid supercapacitors: Design and mechanism insight

With the utilization of sustainable sunlight efficiently, it is of paramount important to develop a new type of electrode for boosting photo-assisted supercapacitor performance. Herein, this work originally designs the Ni35Cu15Zr15Ti35 metallic glass (MG) ribbon as dealloying precursor. Benefiting from the different oxidation behavior of Ni and Cu metals during the dealloying and anodizing processes, a new type of multi-layered porous hybrid photoelectrode (namely CuxO/np-NiCu@NiCuO/MG, x = 1, 2) that simultaneously achieve the flexible, hierarchical porous structure as well as the NiO/Cu2O heterojunction, are successfully synthesized. An intriguing multi-layered structure consists of the outermost photosensitive CuxO nanowire layer formed by the anodizing technique, the nanoporous NiCu@NiCuO layer just beneath the nanowire layer via the dealloying as well as the glass central layer offering an excellent flexibility. In particular, 3D interconnected hierarchical porous structure is benefit to the penetration and utilization of visible light efficiently. The photoelectrode demonstrates a maximum specific capacitance of 1182.2 F cm−3 with light irradiation, which is 18% higher than that without light. This photo-assisting charging for the supercapacitor is ascribed to the combination of photosensitive CuxO and pseudocapacitive NiO components. Moreover, the photoelectrode exhibits an excellent flexibility and the photocurrent response is basically unchanged after bending for 1000 times. The aqueous supercapacitor shows a maximum energy density of 44.9 mWh cm−3 under light. This work provides new insights into the development of next generation wearable photo-assisted supercapacitor.

Increased ductility of Ni-based metallic glass ribbon pre-annealed at β-relaxation temperature

Increased ductility of Ni-based metallic glass ribbon pre-annealed at β-relaxation temperature

Correlation of Magnetomechanical Coupling and Damping in Fe80Si9B11 Metallic Glass Ribbons.

Understanding the correlation between magnetomechanical coupling factors (k) and damping factors (Q-1) is a key pathway toward enhancing the magnetomechanical power conversion efficiency in laminated magnetoelectric (ME) composites by manipulating the magnetic and mechanical properties of Fe-based amorphous metals through engineering. The k and Q-1 factors of FeSiB amorphous ribbons annealed in air at different temperatures are investigated. It is found that k and Q-1 factors are affected by both magnetic and elastic properties. The magnetic and elastic properties are characterized in terms of the magnetomechanical power efficiency for low-temperature annealing. The k and Q-1 of FeSiB-based epoxied laminates with different stacking numbers show that a -3 dB bandwidth and Young's modulus are expressed in terms of the magnetomechanical power efficiency for high lamination stacking.

Toxic element-free Ti-based metallic glass ribbons with precious metal additions

We introduce four new biocompatible toxic element-free Ti-based metallic glass (MG) compositions with constant metalloid (Si10B5) and varying precious metal (PM) contents for simultaneous improvement in glass-forming ability (GFA) and corrosion properties. Being completely free from cytotoxic elements like Cu, Ni, or Be, which are indispensable for Ti-based bulk metallic glass production, limits the GFA of the studied alloys significantly. However, avoiding these elements also realizes an unprecedented corrosion resistance in simulated body fluids, which supports the potential utilization of the alloys as long-lasting dental implant material. The novel Ti60Zr15Si10B5Pd10, Ti60Zr15Si10B5Pt10, Ti60Zr15Si10B5Pd5Pt5, Ti60Zr15Si10B5Pd5Au5 alloys are obtained in ribbon form using conventional single-roller melt spinning. The effect of the PM additions on the GFA and corrosion resistance of the alloys is investigated comparatively with each other by synchrotron X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and cyclic polarization tests. Further, their Vickers hardness values are deduced using an ultra-sensitive micro indentation method, and the findings are discussed based on the composition dependence. It was found that the Ti60Zr15Si10B5Pd5Pt5 alloy presents a promising GFA while showing outstanding corrosion resistance in a simulated body fluid at 310 K.

Excellent Magnetocaloric Performance of the Fe87Ce13-xBx (x = 5, 6, 7) Metallic Glasses and Their Composite.

The novel Fe87Ce13-xBx (x = 5, 6, 7) metallic glass (MG) ribbons were fabricated in this work. The compositional dependence of glass forming ability (GFA), magnetic and magnetocaloric properties of these ternary MGs, and the mechanism involved was investigated. The GFA and Curie temperature (Tc) of the MG ribbons were found to improve with the boron content, and the peak value of magnetic entropy change (-ΔSmpeak) reaches a maximum of 3.88 J/(kg × K) under 5 T when x = 6. Based on the three results, we designed an amorphous composite that exhibits a table-shape magnetic entropy change (-ΔSm) profile with a rather high average -ΔSm (-ΔSmaverage~3.29 J/(kg × K) under 5 T) from 282.5 K to 320 K, which makes it a potential candidate for the highly efficient refrigerant in a domestic magnetic refrigeration appliance.

Improved ductility of annealed Fe-based metallic glass with good soft magnetic property by cryogenic thermal cycling

The brittleness after annealing treatment severely restricts the subsequent processing and application of Fe-based magnetic metallic glass. Through proper annealing treatment combined with cryogenic thermal cycling, we obtained excellent comprehensive properties of Fe-based metallic glass ribbons with not only good soft magnetic properties but also high bending deformation ability. After thermal cycling, the sample rejuvenated with higher energy state and larger size of soft regions, which facilitated the initiation and branching of shear bands, leading to the improvement of bending plasticity. Although the large soft regions may act as pining sites for domain walls, the domain structure and coercivity of the sample remained nearly identical because of the reduced number of crystal-like structures. Our study indicates that the cryogenic thermal cycling is an effective method to regulate mechanical and magnetic properties, which makes it powerful means to obtain excellent performance of Fe-based magnetic metallic glasses.

Short-range order patterns in Mg66Zn29Ca5 metallic glass: Phase transformations and crystallization kinetics

Thanks to outstanding mechanical and chemical properties, metallic glasses have been recently alluring for biomedical applications. However, inadequate knowledge of atomic rearrangements as well as kinetics and mechanisms of crystallization prevents further microstructure improvement controlling the properties. In this work, we reveal that hierarchical transformations happen during the crystallization of Mg66Zn29Ca5 metallic glass ribbons which were investigated using differential scanning calorimetry (DSC), electron microscopy (SEM and TEM), and X-ray diffraction (XRD). The activation energies corresponding to the crystallization of the glassy ribbons were evaluated by different thermodynamic models, i.e., Kissinger, and Augis and Bennett analysis. Our findings prove the formation of short-range order patterns in Mg66Zn29Ca5 metallic glass with a unit size of ∼ 0.247 nm. Furthermore, the applied heating rate affects the glass transformation only slightly but accelerates the growth process quickly. The phase transformations occurring in annealed samples were studied by XRD, proving that crystallization starts with the formation of α-Mg + metastable Mg51Zn20. The metastable Mg51Zn20 gradually transfers to Mg7Zn3 with increasing temperature, and also Ca2Mg5Zn13 precipitates. Close to the end of crystallization, Ca2Mg6Zn3 precipitates by consuming Ca2Mg5Zn13. The Johnson–Mehl–Avrami–Kolmogorov (JMAK) model was employed to obtain the Avrami exponent of the crystallization reaction. The average slope of the Avrami plots is close to 2, indicating that crystallization progresses with diffusional growth and decreasing nucleation rate.

Crystallization discrepancies in Mg65Zn30Ca5 metallic glass ribbon and thin film revealed by nanocalorimetry

In this study, ribbons and thin films of Mg65Zn30Ca5 (at.%) metallic glass were prepared by melt-spinning and magnetron sputtering deposition techniques, respectively. With nanocalorimetry and structural characterization, the rapid crystallization mechanisms of the Mg65Zn30Ca5 ribbon and thin film were evaluated comparatively. The metallic glass thin film has a lower crystallization temperature but a higher apparent activation energy compared to the ribbon. The granular and hierarchical surface of the film promotes heterogeneous nucleation, leading to a lower crystallization temperature. The crystal nucleation and growth processes are analyzed using the Johnson-Mehl-Avrami equation. Compared with the ribbon, whose crystallization is dominated by the growth of pre-existing nuclei, both nucleation and crystal growth occur during the crystallization of the thin film, leading to a higher activation energy. With respect to the ribbon, the crystal growth rate of the thin film is exceptionally higher because of the formation of ordered microstructures inside the film.

Studies on Metallic Glasses in Utsunomiya University

Studies on dissimilar metal welding and mechanical fastening using metallic glasses in Utsunomiya University have been introduced. Metallic glass ribbons placed between the two dissimilar metal plates become supercooled liquid with low viscosity by resistance welding and promote supercooling at the nuggets. As a consequence, the residual stress at the welding boundary and the formation of brittle intermetallic compounds are suppressed, resulting in excellent dissimilar resistance welding with high joint strength and high reproducibility. Mechanical fastening of two metal plates is also demonstrated by resistance heating and viscous flow forming of metallic glass rivets. Producing metallic glass rivets using bulk metallic glasses by a resistance heating is now under examination.

Repairing surface defects of Zr-based metallic glass ribbons by nanosecond pulsed laser irradiation

The metallic glass ribbons (MGRs) industrially produced by the single roller melt-spun method have many surface defects such as pits and scratches. In this study, it was attempted to repair the surface defects of Zr-based MGRs via nanosecond pulsed laser irradiation. The experimental results showed that the roughness of laser-repaired surfaces was significantly reduced compared to the melt-spun surface, and the surface topographies and morphologies were sensitive to the laser parameters. With optimal laser parameters, the smooth and defect-free surface could be achieved. This work offers a convenient and high-efficiency approach for repairing the surface defects of MGRs.