The purpose of this paper was to investigate the effect of a high-energy milling (HEM) process on the particle morphology and the correlation between a thermal treatment and tetragonal/monoclinic nanostructured zirconia powders obtained by a precipitation process. To eliminate chloride residue ions from hydrous zirconia, a modified washing method was used. It was found that the used washing method was effective in removing the chloride from the precipitated gel. In order to investigate the effect of a pre-milling process on the particle morphology of the precipitate, dried Zr(OH)4 was milled using a HEM machine with distilled water. The particle size of the Zr(OH)4 powder exposed to HEM reduced to 100~150 nm, whereas that of fresh Zr(OH)4 powder without a pre-milling process had a large and irregular size of 100 nm~1.5 μm. Additionally, modified heat treatment process was proposed to achieve nano-sized zirconia having a pure monoclinic phase. It was evident that two-step calcining process was effective in perfectly eliminating the tetragonal phase, having a small average particle of ~100 nm with good uniformity compared to the sample calcined by a single-step process, showing a large average particle size of ~300 nm with an irregular particle shape and a broad particle size distribution. The modified method is considered to be a promising process for nano-sized zirconia having a fully monoclinic phase.
As continued scaling becomes increasingly difficult, 3D integration has emerged as a viable solution to achieve higher bandwidths and good power efficiency. 3D integration can be defined as a technology involving the stacking of multiple processed wafers containing integrated circuits on top of each other with vertical interconnects between the wafers. This type of 3D structure can improve performance levels, enable the integration of devices with incompatible process flows, and reduce form factors. Through silicon vias (TSVs), which directly connect stacked structures die-to-die, are an enabling technology for future 3D integrated systems. TSVs filled with copper using an electro-plating method are investigated in this study. DC and pulses are used as a current source for the electro-plating process as a means of via filling. A TiN barrier and Ru seed layers are deposited by plasma-enhanced atomic layer deposition (PEALD) with thicknesses of 10 and 30 nm, respectively. All samples electroplated by the DC current showed defects, even with additives. However, the samples electroplated by the pulse current showed defect-free super-filled via structures. The optimized condition for defect-free bottom-up super-filling was established by adjusting the additive concentrations in the basic plating solution of copper sulfate. The optimized concentrations of JGB and SPS were found to be 10 and 20 ppm, respectively.
The hardenability of low-carbon boron steels with different molybdenum and chromium contents was investigated using dilatometry, microstructural observations and secondary ion mass spectroscopy (SIMS), and then discussed in terms of the segregation and precipitation behaviors of boron. The hardenability was quantitatively evaluated by a critical cooling rate obtained from the hardness distribution plotted as a function of cooling rate. It was found that the molybdenum addition was more effective than the chromium addition to increase the hardenability of boron steels, in contrast to boron-free steels. The addition of 0.2 wt.% molybdenum completely suppressed the formation of eutectoid ferrite, even at the slow cooling rate of 0.2˚C/s, while the addition of 0.5 wt.% chromium did this at cooling rates above 3˚C/s. The SIMS analysis results to observe the boron distribution at the austenite grain boundaries confirmed that the addition of 0.2 wt.% molybdenum effectively increased the hardenability of boron steels, as the boron atoms were significantly segregated to the austenite grain boundaries without the precipitation of borocarbide, thus retarding the austenite-to-ferrite transformation compared to the addition of 0.5 wt.% chromium. On the other hand, the synergistic effect of molybdenum and boron on the hardenability of boron steels could be explained from thermodynamic and kinetic perspectives.
A 90 wt% Mg-10 wt% NbF5 sample was prepared by mechanical milling under H2 (reactive mechanical grinding). Its hydriding and dehydriding properties were then examined. Activation of the 90 wt% Mg-10 wt% NbF5 sample was not required. At n=1, the sample absorbed 3.11 wt% H for 2.5 min, 3.55 wt% H for 5 min, 3.86 wt% H for 10 min, and 4.23 wt% H for 30 min at 593K under 12 bar H2. At n=1, the sample desorbed 0.17 wt% H for 5 min, 0.74 wt% H for 10 min, 2.03 wt% H for 30 min, and 2.81 wt% H for 60 min at 593K under 1.0 bar H2. The XRD pattern of the 90 wt% Mg-10 wt% NbF5 after reactive mechanical grinding showed Mg, β-MgH2 and small amounts of γ-MgH2, NbH2, MgF2 and NbF3. The XRD pattern of the 90 wt% Mg-10 wt% NbF5 dehydrided at n=3 revealed Mg, β-MgH2, a small amount of MgO and very small amounts of MgH2 and NbH2. The 90 wt% Mg-10 wt% NbF5 had a higher initial hydriding rate and a larger quantity of hydrogen absorbed for 60 min than the 90 wt% Mg-10 wt% MnO and the 90 wt% Mg-10 wt% Fe2O3, which were reported to have quite high hydriding rates and/or dehydriding rates. The 90 wt% Mg-10 wt% NbF5 had a higher initial dehydriding rate (after an incubation period) and a larger quantity of hydrogen desorbed for 60 min than the 90 wt% Mg-10 wt% MnO and the 90 wt% Mg-10 wt% Fe2O3.
The deformation properties of a TiC-Mo eutectic composite were investigated in a compression test at temperaturesranging from room temperature to 2053K and at strain rates ranging from 3.9×10−5s−1 to 4.9×10−3s−1. It was found that thismaterial shows excellent high-temperature strength as well as appreciable room-temperature toughness, suggesting that thematerial is a good candidate for high-temperature application as a structure material. At a low-temperature, high strength isobserved. The deformation behavior is different among the three temperature ranges tested here, i.e., low, intermediate and high.At an intermediate temperature, no yield drop occurs, and from the beginning the work hardening level is high. At a hightemperature, a yield drop occurs again, after which deformation proceeds with nearly constant stress. The temperature- andyield-stress-dependence of the strain is the strongest in this case among the three temperature ranges. The observed high-temperature deformation behavior suggests that the excellent high-temperature strength is due to the constraining of thedeformation in the Mo phase by the thin TiC components, which is considerably stronger than bulk TiC. It is also concludedthat the appreciable room-temperature toughness is ascribed to the frequent branching of crack paths as well as to the plasticdeformation of the Mo phase.
The milling and particulate characteristics of Al alloy-Al2O3 powder mixtures for a reaction-bonded Al2O3 (RBAO) process were studied. A commercially available prealloyed Al powder with Zn, Mg, Cu and Cr alloying elements (7475 series) was mixed with a calcined sinter-active Al2O3 powder and then milled in centrifugal milling equipment for ~48 hrs. The Al alloy-Al2O3 powder mixtures after milling were characterized and evaluated in various ways to reveal their particulate characteristics during milling. The milling efficiency of the Al alloy increased with a longer milling time. Comminution of the Al alloy particles started with its elongation, showing a high aspect ratio. With a longer milling time, the elongated Al alloy particle changed in terms of its shape and size, becoming equiaxially fine particles. Regardless of the milling efficiency of the Al alloy particles, all of the Al alloy particles repeatedly experienced strong plastic deformation during milling, giving rise to higher density of surface defects, such as microcracks, and leading to higher residual microstress within the Al alloy particles. The chemical reactions, oxidation behavior and hydration behavior of the Al alloy particles and the hydrolysis characteristics of their reaction with the environment were also observed during the milling process and during the subsequent powder handling steps.
To observe the formation of defects at the interface between an oxide semiconductor and SiO2, ZnO was preparedon SiO2 with various oxygen gas flow rates by RF magnetron sputtering deposition. The crystallinity of ZnO depends on thecharacteristic of the surface of the substrate. The crystallinity of ZnO on a Si wafer increased due to the activation of ionicinteractions after an annealing process, whereas that of ZnO on SiO2 changed due to the various types of defects which hadformed as a result of the deposition conditions and the annealing process. To observe the chemical shift to understand of defectdeformations at the interface between the ZnO and SiO2, the O 1s electron spectra were convoluted into three sub-peaks bya Gaussian fitting. The O 1s electron spectra consisted of three peaks as metal oxygen (at 530.5eV), O2− ions in an oxygen-deficient region (at 531.66eV) and OH bonding (at 532.5eV). In view of the crystallinity from the peak (103) in the XRDpattern, the metal oxygen increased with a decrease in the crystallinity. However, the low FWHM (full width at half maximum)at the (103) plane caused by the high crystallinity depended on the increment of the oxygen vacancies at 531.66eV due tothe generation of O2− ions in the oxygen-deficient region formed by thermal activation energy.
The printing of nanomaterials onto certain substrates is one of the key technologies behind high-speed interconnection and high-performance electronic devices. For the printing of next-generation electronic devices, a printing process which can be applied to a flexible substrate is needed. A printing process on a flexible substrate requires a lowtemperature, non-vacuum process due to the physical properties of the substrate. In this study, we obtained well-ordered Ag nanowires using modified gravure printing techniques. Ag nanowires are synthesized by a silver nitrate (AgNO3) reduction process in an ethylene glycol solution. Ag nanowires were well aligned by hydrodynamic force on a micro-engraved Si substrate. With the three-dimensional structure of polydimethylsiloxane (PDMS), which has an inverse morphology relative to the micro-engraved Si substrate, the sub-micron alignment of Ag nanowires is possible. This technique can solve the performance problems associated with conventional organic materials. Also, given that this technique enables large-area printing, it has great applicability not only as a next-generation printing technology but also in a range of other fields.
Graphene oxide powders prepared by two different drying processes, freeze drying and spray drying, were studied to compare the effect of the drying method on the physical properties of graphene oxide powder. The graphene oxide dispersion was prepared from graphite by chemical delamination with the aid of sulfuric acid and permanganic acid, and the dispersion was further washed and re-dispersed in a mixed solvent of water and isopropyl alcohol. A freeze drying method can feasibly minimize damage to the sample, but it requires a long process time. In contrast, spray drying is able to remove a solvent in a relatively short time, though this process requires exposure to a high temperature for a rapid evaporation of the solvent. The powders prepared by freeze drying and spray drying were characterized and compared by Raman spectroscopy, X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and by an elemental analysis. The graphene oxide powders showed similar chemical compositions; however, the morphologies of the powders differed in that the graphene oxide prepared by spray drying had a winkled morphology and a higher apparent density compared to the powder prepared by freeze drying. The graphene oxide powders were reduced at 900˚C in an atmosphere of N2. The effect of the drying process on the properties of the reduced graphene oxide was examined by SEM, TEM and Raman spectroscopy.
CSA, a cement mineral compound that is mainly composed of 3CaO·3Al2O3·CaSO4, generates ettringite as a hydration product after a reaction with glass (lime), gypsum and water to speed up the hardening process and enhance the strength and degree of expansion. When used as a cement admixture, there is increased production of ettringite, which can improve the initial strength in the first three days and ameliorate the reduction in the initial strength caused by the use of fly ash in particular. In this study, a hydrate analysis was performed using XRD and SEM after substitution with fly ash (30%) and CSA (8%) with the goal of observing the effect of CSA on the initial strength of a cement mixture containing fly ash. The results of the analysis showed that an addition of CSA promoted the production of ettringite and improved the initial strength, resulting in the generation of hydrates, which can effectively enhance the long-term strength of these materials.