Developing and characterizing bulk metallic glasses for extreme applications

Metallic glasses have typically been treated as a “one size fits all” type of material. Every alloy is considered to have high strength, high hardness, large elastic limits, corrosion resistance, etc. However, similar to traditional crystalline materials, properties are strongly dependent upon the constituent elements, how it was processed, and the conditions under which it will be used. An important distinction which can be made is between metallic glasses and their composites. Charpy impact toughness measurements are performed to determine the effect processing and microstructure have on bulk metallic glass matrix composites (BMGMCs). Samples are suction cast, machined from commercial plates, and semi-solidly forged (SSF). The SSF specimens have been found to have the highest impact toughness due to the coarsening of the dendrites, which occurs during the semi-solid processing stages. Ductile to brittle transition (DTBT) temperatures are measured for a BMGMC. While at room temperature the BMGMC is highly toughened compared to a fully glassy alloy, it undergoes a DTBT by 250 K. At this point, its impact toughness mirrors that of the constituent glassy matrix. In the following chapter, BMGMCs are shown to have the capability of being capacitively welded to form single, monolithic structures. Shear measurements are performed across welded samples, and, at sufficient weld energies, are found to retain the strength of the parent alloy. Cross-sections are inspected via SEM and no visible crystallization of the matrix occurs.

Next, metallic glasses and BMGMCs are formed into sheets and eggbox structures are tested in hypervelocity impacts. Metallic glasses are ideal candidates for protection against micrometeorite orbital debris due to their high hardness and relatively low density. A flat single layer, flat BMG is compared to a BMGMC eggbox and the latter creates a more diffuse projectile cloud after penetration. A three tiered eggbox structure is also tested by firing a 3.17 mm aluminum sphere at 2.7 km/s at it. The projectile penetrates the first two layers, but is successfully contained by the third.

A large series of metallic glass alloys are created and their wear loss is measured in a pin on disk test. Wear is found to vary dramatically among different metallic glasses, with some considerably outperforming the current state-of-the-art crystalline material (most notably Cu₄₃Zr₄₃Al₇Be₇). Others, on the other hand, suffered extensive wear loss. Commercially available Vitreloy 1 lost nearly three times as much mass in wear as alloy prepared in a laboratory setting. No conclusive correlations can be found between any set of mechanical properties (hardness, density, elastic, bulk, or shear modulus, Poisson’s ratio, frictional force, and run in time) and wear loss. Heat treatments are performed on Vitreloy 1 and Cu₄₃Zr₄₃Al₇Be₇. Anneals near the glass transition temperature are found to increase hardness slightly, but decrease wear loss significantly. Crystallization of both alloys leads to dramatic increases in wear resistance. Finally, wear tests under vacuum are performed on the two alloys above. Vitreloy 1 experiences a dramatic decrease in wear loss, while Cu₄₃Zr₄₃Al₇Be₇ has a moderate increase. Meanwhile, gears are fabricated through three techniques: electrical discharge machining of 1 cm by 3 mm cylinders, semisolid forging, and copper mold suction casting. Initial testing finds the pin on disk test to be an accurate predictor of wear performance in gears.

The final chapter explores an exciting technique in the field of additive manufacturing. Laser engineered net shaping (LENS) is a method whereby small amounts of metallic powders are melted by a laser such that shapes and designs can be built layer by layer into a final part. The technique is extended to mixing different powders during melting, so that compositional gradients can be created across a manufactured part. Two compositional gradients are fabricated and characterized. Ti 6Al¬ 4V to pure vanadium was chosen for its combination of high strength and light weight on one end, and high melting point on the other. It was inspected by cross-sectional x-ray diffraction, and only the anticipated phases were present. 304L stainless steel to Invar 36 was created in both pillar and as a radial gradient. It combines strength and weldability along with a zero coefficient of thermal expansion material. Only the austenite phase is found to be present via x-ray diffraction. Coefficient of thermal expansion is measured for four compositions, and it is found to be tunable depending on composition.

I. Reactively sputtered Ti-Si-N thin films for diffusion barrier applications. II. Oxidation, diffusion and crystallization of an amorphous Zr_(60)Al_(15)Ni_(25) alloy.

Films of Ti-Si-N obtained by reactively sputtering a TiSi_2, a Ti_5Si_3, or a Ti_3Si target are either amorphous or nanocrystalline in structure. The atomic density of some films exceeds 10^23 at./cm^3. The room-temperature resistivity of the films increases with the Si and the N content. A thermal treatment in vacuum at 700 °C for 1 hour decreases the resistivity of the Ti-rich films deposited from the Ti_5Si_3 or the Ti_3Si target, but increases that of the Si-rich films deposited from the TiSi_2 target when the nitrogen content exceeds about 30 at. %.

Ti_(34)Si_(23)N_(43) deposited from the Ti_5Si_3 target is an excellent diffusion barrier between Si and Cu. This film is a mixture of nanocrystalline TiN and amorphous SiN_x. Resistivity measurement from 80 K to 1073 K reveals that this film is electrically semiconductor-like as-deposited, and that it becomes metal-like after an hour annealing at 1000 °C in vacuum. A film of about 100 nm thick, with a resistivity of 660 µΩcm, maintains the stability of Si n+p shallow junction diodes with a 400 nm Cu overlayer up to 850 °C upon 30 min vacuum annealing. When used between Si and Al, the maximum temperature of stability is 550 °C for 30 min. This film can be etched in a CF_4/O_2 plasma.

The amorphous ternary metallic alloy Zr_(60)Al_(15)Ni_(25) was oxidized in dry oxygen in the temperature range 310 °C to 410 °C. Rutherford backscattering and cross-sectional transmission electron microscopy studies suggest that during this treatment an amorphous layer of zirconium-aluminum-oxide is formed at the surface. Nickel is depleted from the oxide and enriched in the amorphous alloy below the oxide/alloy interface. The oxide layer thickness grows parabolically with the annealing duration, with a transport constant of 2.8x10^(-5) m^2/s x exp(-1.7 eV/kT). The oxidation rate is most likely controlled by the Ni diffusion in the amorphous alloy.

At later stages of the oxidation process, precipitates of nanocrystalline ZrO_2 appear in the oxide near the interface. Finally, two intermetallic phases nucleate and grow simultaneously in the alloy, one at the interface and one within the alloy.

Welding of Al alloy plates using a novel high-average-power pulsed CO2 laser

A novel high-average-power pulsed CO2 laser with a unique electrode structure is presented. The operation of a 5-kW transverse-flow CO2 laser with the preionized pulse-train switched technique results in pulsation of the laser power, and the average laser power is about 5 kW. The characteristic of this technique is switching the preionized pulses into pulse trains so as to use the small preionized power (hundreds of watts) to control the large main-discharge power (tens of kilowatts). By this means, the cost and the complexity of the power supply are greatly reduced. The welding of LF2, LF21, LD2, and LY12 aluminum alloy plates has been successfully achieved using this laser. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Welding of Al alloy plates using a novel high-average-power pulsed CO2 laser

A novel high-average-power pulsed CO2 laser with a unique electrode structure is presented. The operation of a 5-kW transverse-flow CO2 laser with the preionized pulse-train switched technique results in pulsation of the laser power, and the average laser power is about 5 kW. The characteristic of this technique is switching the preionized pulses into pulse trains so as to use the small preionized power (hundreds of watts) to control the large main-discharge power (tens of kilowatts). By this means, the cost and the complexity of the power supply are greatly reduced. The welding of LF2, LF21, LD2, and LY12 aluminum alloy plates has been successfully achieved using this laser. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Mapping the global flow of aluminum: from liquid aluminum to end-use goods.

Demand for aluminum in final products has increased 30-fold since 1950 to 45 million tonnes per year, with forecasts predicting this exceptional growth to continue so that demand will reach 2-3 times today's levels by 2050. Aluminum production uses 3.5% of global electricity and causes 1% of global CO2 emissions, while meeting a 50% cut in emissions by 2050 against growing demand would require at least a 75% reduction in CO2 emissions per tonne of aluminum produced--a challenging prospect. In this paper we trace the global flows of aluminum from liquid metal to final products, revealing for the first time a complete map of the aluminum system and providing a basis for future study of the emissions abatement potential of material efficiency. The resulting Sankey diagram also draws attention to two key issues. First, around half of all liquid aluminum (~39 Mt) produced each year never reaches a final product, and a detailed discussion of these high yield losses shows significant opportunities for improvement. Second, aluminum recycling, which avoids the high energy costs and emissions of electrolysis, requires signification "dilution" (~ 8 Mt) and "cascade" (~ 6 Mt) flows of higher aluminum grades to make up for the shortfall in scrap supply and to obtain the desired alloy mix, increasing the energy required for recycling.

Surface-enhanced resonant Raman spectroscopy (SERRS) of single-walled carbon nanotubes absorbed on the Ag-coated anodic aluminum oxide (AAO) surface

In this paper, we developed a new kind of substrate, the silver-coated anodic aluminum oxide (AAO), to investigate the characters of surface-enhanced resonant Raman scattering (SERRS) of the dilute single-walled carbon nanotubes. Homogeneous Ag-coated AAO substrate was obtained by decomposing the AgNO3 on the surface of AAO. single-walled carbon nanotubes (SWNTs) were directly grown onto this substrate through floating catalyst chemical vapor deposition method (CVD). SERRS of SWNTs was carried out using several different wavelength lasers. The bands coming from metallic SWNTs were significantly enhanced. The two SERRS mechanisms, the "electromagnetic" and "chemical" mechanism, were mainly responsible for the experiment results. (c) 2005 Elsevier B.V. All rights reserved.

Silver nanocluster-based fluorescent sensors for sensitive detection of Cu(II)

In this work, we report the first application of water-soluble fluorescent Ag nanoclusters in fluorescent sensors. The fluorescence of poly(methacrylic acid) (PMAA)-templated Ag nanoclusters was found to be quenched effectively by Cu2+, but not when other common metal ions were present. By virtue of the specific response toward the analyte, a new, simple, and sensitive fluorescent method for detecting Cu2+ has been developed based on Ag nanoclusters.

Glass formation ability and mechanical properties of Ti40Cu40Zr10Ni10 alloy

Melt-spun ribbon and bulk samples in cylindrical rod form with diameter ranging from 2 mm to 4 mm of Ti40Cu40Zr10Ni10 alloy were prepared by melt-spinning technique and copper mould casting method, respectively. The microstructure, thermal stability and mechanical properties of the bulk samples were investigated. A completely glassy single phase is formed in the 2 mm rod sample. Increasing the diameter of the rod samples resulted in the formation of CuTi crystalline phase in the 3 mm and 4 mm rod samples.

Wear mechanism map of uncoated HSS tools during drilling die-cast magnesium alloy

A wear mechanism map of uncoated high-speed steel (HSS) tools was constructed under the conditions of dry-drilling die-cast magnesium alloys. Three wear mechanisms appear in the map based on the microanalysis of drilled HSS tools by SEM, including adhesive wear, abrasive wear and diffusion wear. In the map, there exists a minor wear region which is called "safety zone". This wear mechanism map will be a good reference for choosing suitable drilling parameters when drilling die-cast magnesium alloys.

Dendrimers as "controllers" for modulation of electrodeposited silver nanostructures

Electrodeposition of silver nanostructures on a polyamidoamine (PAMAM) dendrimers-modified surface has been reported. The assembled PAMAM monolayer film was used as a substrate for electrodeposition. We found that the PAMAM dendrimers obviously affected nucleation growth and silver nanostructures (spherical, dendritic and "fish bone" shapes) were obtained, which were different from those deposited on unmodified surfaces. It was attributed to the unique structures and properties of PAMAM dendrimers compared with linear polymers.

Large-Scale and Template-Free Growth of Free-Standing Single-Crystalline Dendritic Ag/Pd Alloy Nanostructure Arrays

Large-scale arrays consist of dendritic single-crystalline Ag/Pd alloy nanostructures are synthesized for the first time. A simple galvanic replacement reaction is introduced to grow these arrays directly on Ag substrates. The morphology of the products strongly depended on the reaction temperature and the concentration of H2PdCl4 solution. The mechanism of the formation of alloy and the dendritic morphology has been discussed. These alloy arrays exhibit high surface-enhanced Raman scattering (SERS) activity and may have potential applications in investigation of "in situ" Pd catalytic reactions using SERS. Moreover, electrocatalytic measurements suggest that the obtained dendritic Ag/Pd alloy nanostructures exhibit electrocatytic activity toward the oxidation of formic acid.

Realization of negative differential resistance and switching devices based on copper phthalocyanine by the control of evaporation rate

We have observed, respectively, a negative differential resistance (NDR) and switching conduction in current-voltage (I-V) characteristics of organic diodes based on copper phthalocyanine (CuPc) film sandwiched between indium-tin-oxide (ITO) and aluminum (Al) by controlling the evaporation rate. The NDR effect is repeatable which can be well, controlled by sweep rate and start voltage, and the switching exhibits write-once-read-many-times (WORM) memory characteristics. The traps in the organic layer and interfacial dipole have been used to explain the NDR effect and switching conduction. This opens up potential applications for CuPc organic semiconductor in low power memory and logic circuits.

The mechanical properties of magnesium matrix composites reinforced with 10 wt.% W14Al86 alloy particles

The Mg-based metal matrix composite reinforced by 10 wt.% W14Al86 alloy particles has been prepared by mechanical alloying and press-forming process. X-ray diffraction studies confirm the formation of the composite. Microstructure characterization of the samples reveals the uniform distribution of fine W14Al86 alloy. Mechanical properties characterization revealed that the reinforcement of W14Al86 alloy lead to a significant increase in hardness and tensile strength of Mg and AZ91.

Fabrication, microstructure and mechanical properties of novel cemented hard alloy obtained by mechanical alloying and hot-pressing sintering

A novel cemented carbides alloy (W0.4Al0.6)C-0.65-Co were prepared by mechanical alloying and hot-pressing sintering in this work. Hot-pressing (HP) as a common technique was performed to fabricate the bulk bodies of the hard alloys. The hardness, bending strength, density of the novel hard alloy are also tested, and it has superior mechanical properties. The hardness of (W0.4Al0.6)C-0.65-Co hard alloy was very high, and the density, operate cost of the novel material were much lower than WC-Co, more important is the aluminum dissolving is not decrease the strength compared with the WC-Co system. There is almost no eta-phase in the (W0.4Al0.6)C-0.65-Co cemented carbides system even the carbon deficient reaches the astonishing value of 35%. This novel property will give us more choice to design and gain new materials that we needed.

Microstructures and properties of melt-spun and as-cast Mg-20Gd binary alloy

Mg-20Gd(%, mass fraction) samples were prepared using melt-spinning and copper mold casting techniques. Microstructures and properties of the Mg-20Gd were investigated. Results show that the melt-spun ribbon is mainly composed of supersaturated alpha-Mg solid solution phase and the as-east ingot mainly contains alpha-Mg solid solution and Mg5Gd phase. The differential scanning calorimeter (DSC) curve of the ribbon exhibits a small exothermic peak in the temperature range from 630 to 680 K, which indicates that the ribbon contains a metastable phase (amorphous). Tensile strength at room temperature of the melt-spun ribbon and as-cast specimen are 308 and 254 MPa, respectively. The elongations of the two samples are less than 2%. The fracture surfaces demonstrate that the fracture mode of the as-cast Mg-20Gd is a typical cleavage fracture and that of the melt-spun sample is a combination of brittle fracture and ductile fracture.