Oxidation-induced superelasticity in metallic glass nanotubes.

Although metallic nanostructures have been attracting tremendous research interest in nanoscience and nanotechnologies, it is known that environmental attacks, such as surface oxidation, can easily initiate cracking on the surface of metals, thus deteriorating their overall functional/structural properties1-3. In sharp contrast, here we report that severely oxidized metallic glass nanotubes can attain an ultrahigh recoverable elastic strain of up to ~14% at room temperature, which outperform bulk metallic glasses, metallic glass nanowires and many other superelastic metals hitherto reported. Through in situ experiments and atomistic simulations, we reveal that the physical mechanisms underpinning the observed superelasticity can be attributed to the formation of a percolating oxide network in metallic glass nanotubes, which not only restricts atomic-scale plastic events during loading but also leads to the recovery of elastic rigidity on unloading. Our discovery implies that oxidation in low-dimensional metallic glasses can result in unique properties for applications in nanodevices.

Negative Effects of Annealed Seed Layer on the Performance of ZnO-Nanorods Based Nitric Oxide Gas Sensor.

Nitric oxide (NO) is a toxic gas, which is dangerous for human health and causes many respiratory infections, poisoning, and lung damage. In this work, we have successfully grown ZnO nanorod film on annealed ZnO seed layer in different ambient temperatures, and the morphology of the nanorods sensing layer that affects the gas sensing response to nitric oxide (NO) gas were investigated. To acknowledge the effect of annealing treatment, the devices were fabricated with annealed seed layers in air and argon ambient at 300 °C and 500 °C for 1 h. To simulate a vertical device structure, a silver nanowire electrode covered in ZnO nanorod film was placed onto the hydrothermal grown ZnO nanorod film. We found that annealing treatment changes the seed layer's grain size and defect concentration and is responsible for this phenomenon. The I-V and gas sensing characteristics were dependent on the oxygen defects concentration and porosity of nanorods to react with the target gas. The resulting as-deposited ZnO seed layer shows better sensing response than that annealed in an air and argon environment due to the nanorod morphology and variation in oxygen defect concentration. At room temperature, the devices show good sensing response to NO concentration of 10 ppb and up to 100 ppb. Shortly, these results can be beneficial in the NO breath detection for patients with chronic inflammatory airway disease, such as asthma.

Cost-effective large-area Ag nanotube arrays for SERS detections: effects of nanotube geometry.

This study demonstrated highly-ordered metallic nanotube arrays (MeNTAs) with a precisely controlled geometric shape to promote surface-enhanced Raman scattering (SERS). Using both simulation and experimental methods, we designed and fabricated MeNTAs with nanotube geometries that possess a large surface area to absorb probe molecules as well as geometric features capable of inducing hot spots for SERS enhancement. The proposed top-down wafer-scale lithographic and sputter-deposition process is a simple and cost-effective approach to the fabrication of 1 mm × 1 mm MeNTA at room temperature. Simulation results of nanotubes with various materials (Au, Ag, and Cu), diameters (100-1500 nm), geometric shapes (circle, equilateral triangle and square) and triangle corner curvatures (ranging from 0 to 300 nm) identified Ag triangles with sharp tips as the geometry best suited to SERS enhancement. The SERS spectra of crystal violet molecules generated from the Ag MeNTAs verified the patterns observed in computational simulations, wherein the effects of MeNTA on SERS decreased with an increase in the size of the nanotubes. Enhancement factor of 1.06 × 109was obtained from our triangular Ag MeNTA, confirming its efficacy as an ultrahigh sensitivity SERS-active substrate.

High-Performance Sensor Based on Thin-Film Metallic Glass/Ultra-nanocrystalline Diamond/ZnO Nanorod Heterostructures for Detection of Hydrogen Gas at Room Temperature.

This article outlines a novel material to enable the detection of hydrogen gas. The material combines thin-film metallic glass (TFMG), ultra-nanocrystalline diamond (UNCD), and ZnO nanorods (ZNRs) and can be used as a device for effective hydrogen gas sensing. Three sensors were fabricated by using combinations of pure ZNRs (Z), UNCD/ZNRs (DZ), and TFMG/UNCD/ZNRs (MDZ). The MDZ device exhibited a performance superior to the other configurations, with a sensing response of 34 % under very low hydrogen gas concentrations (10 ppm) at room temperature. Remarkably, the MDZ-based sensor exhibits an ultra-high sensitivity of 60.5 % under 500 ppm H2 . The MDZ sensor proved very fast in terms of response time (20 s) and recovery time (35 s). In terms of selectivity, the sensors were particularly suited to hydrogen gas. The sensor achieved the same response performance even after two months, thereby demonstrating the superior stability. It is postulated that the superior performance of MDZ can be attributed to defect-related adsorption as well as charge carrier density. This paper also discusses the respective energy band models of these heterostructures and also the interface effect on the gas sensing enhancements. The results indicate that the proposed hybrid TFMG/UNCD/ZNRs nanostructures could be utilized as high-performance hydrogen gas sensors.

Electrochemical nonenzymatic glucose sensors catalyzed by Au nanoclusters on metallic nanotube arrays and polypyrrole nanowires.

Monitoring blood glucose level is critical, since its abnormality leads to diabetes and causes death, even though glucose is essential for human living. Herein, the sensing study was performed on electrochemical nonenzymatic glucose sensors, which are composed of an Au nanocluster (AuNC) catalyst deposited on a metallic nanotube array (MeNTA) and polypyrrole nanowire (PPyNW). The AuNC was produced by irradiating a femtosecond pulse laser to the Au precursor solution, and it is a simple and facile method. The successful deposition of AuNC on both MeNTA and PPyNW was confirmed by means of the surface morphology and the Au content increase. On the exploration by cyclic voltammetry in alkaline condition, AuNC/MeNTA electrodes showed better performance than AuNC/PPyNW electrodes: The former was a remarkable electrocatalytic detector towards glucose oxidation with better sensitivity, lower detection limit, wider linear range, and longer-term stability without interference from potential interfering agents such as ascorbic acid, urea, NaCl, KCl, etc. Moreover, nonenzymatic AuNC/MeNTA electrodes exhibited high precision and accuracy in real human blood samples and, thus, can be a promising candidate in glucose sensing applications.

Effect of a three-dimensional nanotube array substrate on photocatalytic conversion performance of CO2 gas to methanol by amine-loaded CuO/ZnO catalysts.

The photocatalytic conversion of CO2 gas into energy-dense hydrocarbons holds the potential to address both environmental and energy problems. Catalysts consisting of CuO clusters/nanoparticles and ZnO nanorods on a metallic nanotube array (MeNTA) silicon substrate were utilized for CO2 reduction. The surface of the catalysts was modified with 3-amino-propyltriethoxysilane (APTES), the amine terminal of which can selectively bind CO2 gas. When photocatalytic CO2 reduction was performed with varying APTES and CuO contents, the highest methanol production of 4.5 mmol/g(catalyst) was obtained at 10 wt% APTES and 7.5 mM CuO contents. The high yield in the present work in comparison with previous reports is due to some advantages of the present catalytic system such as its enhanced activity, significant selectivity, and easy production: Nanometer-sized CuO produced by femtosecond pulse laser irradiation provides a larger active surface per volume and a free surface without a protector, which is favorable for advancing the catalytic activity. The formation of a heterojunction interface in a nanocomposite of p-type CuO and n-type ZnO increases holes at the valence band level of CuO, resulting in advantageous photovoltaic efficiency. The introduction of APTES on the catalyst surface enhances CO2 adsorption and brings about CO2 gas near the catalyst to accelerate the reaction rate. Finally, a three-dimensional tube array on the substrate enlarges the surface per volume for catalyst-loading compared to the two-dimensional substrate. Thus, the proposed catalytic system consisting of amine-loaded CuO/ZnO constructed on a three-dimensional nanotube array substrate is preferable for the photocatalytic conversion of CO2 gas to methanol.

Preclinical studies of non-stick thin film metallic glass-coated syringe needles.

Our objective in this study was to determine the biocompatibility and hemocompatibility of thin film metallic glass (TFMG) and its potential use in hypodermic needles for intramuscular or intravenous injection. Mouse and rabbit models were employed under approval from the Institutional Animal Care and Use Committee (n = 5/group, two groups in total for both animal models). Platelet-rich plasma (PRP) was collected from the whole blood of rabbits (ear vein) without anti-coagulant for use in in vitro coagulation tests. Histological analysis and optical microscopy were used to assess the endothelial structure of the inner lining of veins after being punctured with needles and detained for 3 days. Histological analysis of ear vein sections revealed that the extent of endothelial damage after puncturing with a TFMG-coated needle was 33% less than that produced by bare needles. Our results confirm that the deposition of a thin TFMG layer (e.g., Zr53Cu33Al9Ta5) on the surface of hypodermic needle can have remarkably clinical benefits, including anti-adhesion, reduced invasion, and minimal endothelial damage. Our results also confirm the good biocompatibility and hemocompatibility of the TFMG coatings.

Metallic glass coating for improving diamond dicing performance.

This is the first report on the coating of diamond dicing blades with metallic glass (MG) coating to reduce chipping when used to cut Si, SiC, sapphire, and patterned sapphire substrates (PSS). The low coefficient-of-friction (CoF) of Zr-based MG-coated dicing blades was shown to reduce the number and size of chips, regardless of the target substrate. Overall, SiC, sapphire and PSS were most affected by chipping, due to the fact that higher cutting forces were needed for the higher hardness of SiC, sapphire and PSS. Compared to the bare blade, the MG coating provided the following reductions in chipping area: Si (~ 23%), SiC (~ 36%), sapphire (~ 45%), and PSS (~ 33%). The proposed coating proved particularly effective in reducing chips of larger size (> 41 µm in chipping width), as indicated by an ~ 80% reduction when cutting sapphire. Small variations in kerf angle and depth demonstrate the durability of the coated blades, which would no doubt enhance consistency in dicing performance and extend the blade lifespan. Finite-element modeling revealed significant reductions in tensile stress and elastic-plastic deformation during dicing, thanks to a lower CoF.

Metallic glass coating for improved needle tattooing performance in reducing trauma: analysis on porcine and pig skins.

The dissemination of tattooing into mainstream culture has raised concerns pertaining to the medical implications of these practices. This paper reports on the coating of tattoo needles with metallic-glass (MG) to reduce trauma to the skin. Extensive experimentation using pork samples and live pigs demonstrated the beneficial effects of non-stick MG coatings. Following 30 insertions into pork skin, significantly less tissue adhered to the MG-coated needles than to uncoated needles. MG-coated needles were also shown to reduce the spread of pigment to the surface of surrounding skin by up to 57%. This resulted in narrower tattoo lines of higher density, indicating that MG-coated needles could be useful in high-resolution tattooing. Histopathological analysis on live pigs revealed severe trauma induced by bare needles, as indicated by the secretion of fluids immediately after tattooing. The wounds formed by coated needles closed within 2 h after tattooing; however, those formed by bare needles remained open for at least 2 h and inflammation was still observed after 3 days. At 5 days after tattooing, skin punctured by the coated needle was entirely healed, whereas skin punctured by the bare needle was still covered with scabs. In addition to the medical benefits, it appears that MG-coated needles could improve the quality of tattoos, based on the fact that the amount of pigment retained in the skin is inversely proportional to the trauma caused by needles.

Coating Cutting Blades with Thin-Film Metallic Glass to Enhance Sharpness.

In this study, we sought to enhance the cutting properties of the various blades by coating them with Zr- and Fe-based thin film metallic glasses (TFMGs) to a thickness of 234-255 nm via sputter deposition. In oil-repellency/sliding tests on kitchen blades, the sliding angle and friction forces were as follows: bare blades (31.6°) and (35 µN), Ti-coated blades (20.3°) and (23.7 µN), and Z-TFMG coated blades (16.2°) and (19.2 µN). Comparisons were conducted with bare blades and those with a Teflon coating (a low-friction material commonly used for the coating of microtome blades). We also found that the Teflon coating reduced the cutting forces of an uncoated microtome blade by ~80%, whereas the proposed Z-TFMG achieved a ~51% reduction. The Z-TFMG presented no indications of delamination after being used 30 times for cutting; however, the Teflon coating proved highly susceptible to peeling and the bare blade was affected by surface staining. These results demonstrate the efficacy of the TFMG coating in terms of low friction, non-stick performance, and substrate adhesion. The performance of Z-TFMG and F-TFMG was also evaluated in split-thickness skin graft surgery using dermatome blades aimed at elucidating the influence of TFMG coatings on the healing of surgical incisions. When tested repeatedly on hairless skin, the surface roughness of uncoated blades increased by approximately 70%, whereas the surface roughness of TFMG-coated blades increases by only 8.6%. In the presence of hair, the surface roughness of uncoated blades increased by approximately ~108%, whereas the surface roughness of TFMG-coated blades increases by only ~23%. By Day 7, the wounds produced using TFMG-coated blades were noticeably smaller than those produced using uncoated blades, and these effects were particularly evident in hairy samples. This is a clear demonstration of the efficacy of TFMG surface coatings in preserving the cutting quality of surgical instruments.

Fabrication of ordered metallic glass nanotube arrays for label-free biosensing with diffractive reflectance.

In this study, a photoresist template with well-defined contact hole array was fabricated, to which radio frequency magnetron sputtering process was then applied to deposit an alloyed Zr55Cu30Al10Ni5 target, and finally resulted in ordered metallic glass nanotube (MGNT) arrays after removal of the photoresist template. The thickness of the MGNT walls increased from 98 to 126nm upon increasing the deposition time from 225 to 675s. The wall thickness of the MGNT arrays also increased while the dimensions of MGNT reduced under the same deposition condition. The MGNT could be filled with biomacromolecules to change the effective refractive index. The air fraction of the medium layer were evaluated through static water contact angle measurements and, thereby, the effective refractive indices the transverse magnetic (TM) and transverse electric (TE) polarized modes were calculated. A standard biotin-streptavidin affinity model was tested using the MGNT arrays and the fundamental response of the system was investigated. Results show that filling the MGNT with streptavidin altered the effective refractive index of the layer, the angle of reflectance and color changes identified by an L*a*b* color space and color circle on an a*b* chromaticity diagram. The limit of detection (LOD) of the MGNT arrays for detection of streptavidin was estimated as 25nM, with a detection time of 10min. Thus, the MGNT arrays may be used as a versatile platform for high-sensitive label-free optical biosensing.

Fabrication of an artificial nanosucker device with a large area nanotube array of metallic glass.

The concurrent attachment and detachment movements of geckos on virtually any type of surface via their foot pads have inspired us to develop a thermal device with numerous arrangements of a multi-layer thin film together with electrodes that can help modify the temperature of the surface via application of a voltage. A sequential fabrication process was employed on a large-scale integration to generate well-defined contact hole arrays of photoresist for use as templates on the electrode-based device. The photoresist templates were then subjected to sputter deposition of the metallic glass Zr55Cu30Al10Ni5. Consequently, a metallic glass nanotube (MGNT) array having a nominal wall thickness of 100 nm was obtained after removal of the photoresist template. When a water droplet was placed on the MGNT array, close nanochambers of metallic glass were formed. By applying voltage, the surface was heated to increase the pressure inside the nanochambers; this generated an expanding force that raised the droplet; thus, the static water contact angle (SWCA) was increased. In contrast, a sucking force was generated during surface cooling, which decreased the SWCA. Our fabrication strategy exploits the MGNT array surface as nanosuckers, which can mimic the climbing aptitude of geckos as they attach to (>10 N m-2) and detach from (0.26 N m-2) surfaces at 0.5 and 3 V of applied voltage, respectively. Thus, the climbing aptitude of geckos can be mimicked by employing the processing strategy presented herein for the development of artificial foot pads.

Few-Layer Thin-Film Metallic Glass-Enhanced Optical Properties of ZnO Nanostructures.

A few layers of Cu-based (Cu47Zr42Al7Ti4) thin-film metallic glasses (TFMGs) were sputtered on hydrothermally synthesized ZnO nanowires/glass and ZnO nanotubes/glass to fabricate UV photodetectors. The few layers of Cu-based TFMG are ultrathin at ∼0.98 nm and have a noncrystalline metal structure according to X-ray diffraction, Raman, photoluminescence, and high-temperature transmission electron microscopy verification. The photoresponse performance of the coated few-layers Cu-TFMG samples was enhanced 1680-7700% compared with the noncoated sample. The few-layers Cu-TFMG has high transmittance ∼90% in the visible band and creates a large capacitor to absorb UV photocurrent and release dark current.

Thin-film metallic glass: an effective diffusion barrier for Se-doped AgSbTe2 thermoelectric modules.

The thermal stability of joints in thermoelectric (TE) modules, which are degraded during interdiffusion between the TE material and the contacting metal, needs to be addressed in order to utilize TE technology for competitive, sustainable energy applications. Herein, we deposit a 200 nm-thick Zr-based thin-film metallic glass (TFMG), which acts as an effective diffusion barrier layer with low electrical contact resistivity, on a high-zT Se-doped AgSbTe2 substrate. The reaction couples structured with TFMG/TE are annealed at 673 K for 8-360 hours and analyzed by electron microscopy. No observable IMCs (intermetallic compounds) are formed at the TFMG/TE interface, suggesting the effective inhibition of atomic diffusion that may be attributed to the grain-boundary-free structure of TFMG. The minor amount of Se acts as a tracer species, and a homogeneous Se-rich region is found nearing the TFMG/TE interface, which guarantees satisfactory bonding at the joint. The diffusion of Se, which has the smallest atomic volume of all the elements from the TE substrate, is found to follow Fick's second law. The calculated diffusivity (D) of Se in TFMG falls in the range of D~10-20-10-23(m2/s), which is 106~107 and 1012~1013 times smaller than those of Ni [10-14-10-17(m2/s)] and Cu [10-8-10-11(m2/s)] in Bi2Te3, respectively.

Non-stick syringe needles: Beneficial effects of thin film metallic glass coating.

This paper reports on the use of Zr-based (Zr53Cu33Al9Ta5) thin film metallic glass (TFMG) for the coating of syringe needles and compares the results with those obtained using titanium nitride and pure titanium coatings. TFMG coatings were shown to reduce insertion forces by ∼66% and retraction forces by ∼72%, when tested using polyurethane rubber block. The benefits of TFMG-coated needles were also observed when tested using muscle tissue from pigs. In nano-scratch tests, the TFMG coatings achieved a coefficient of friction (COF) of just ∼0.05, which is about one order of magnitude lower than those of other coatings. Finite-element modeling also indicates a significant reduction in injection and retraction forces. The COF can be attributed to the absence of grain boundaries in the TFMG coating as well as a smooth surface morphology and low surface free energy.