Two types of nanoclusters, termed Cluster (1) and Cluster (2) here, both play an important role in the age-hardening behavior in Al-Mg-Si alloys. Small amounts of additions of Cu and Ag affect the formation of nanoclusters. Two exothermic peaks were clearly detected in differential scanning calorimetry(DSC) curves by means of peak separation by the Gaussian method in the base, Cu-added, Ag-added and Cu-Ag-added Al-Mg-Si alloys. The formation of nanoclusters in the initial stage of natural aging was suppressed in the Ag-added and Cu-Ag-added alloys, while the formation of nanoclusters was enhanced at an aging time longer than 259.2 ks(3 days) of natural aging with the addition Cu and Ag. The formation of nanoclusters while aging at 100˚C was accelerated in the Cu-added, Ag-added and Cu-Ag-added alloys due to the attractive interaction between the Cu and Ag atoms and the Mg atoms. The influence of additions of Cu and Ag on the clustering behavior during low-temperature aging was well characterized based on the interaction energies among solute atoms and on vacancies derived from the first-principle calculation of the full-potential Korrinaga-Kohn-Rostoker(FPKKR)-Green function method. The effects of low Cu and Ag additions on the formation of nanoclusters were also discussed based on the age-hardening phenomena.
Recently, the demand for the miniaturization of printed circuit boards has been increasing, as electronic devices have been sharply downsized. Conventional multi-layered PCBs are limited in terms their use with higher packaging densities. Therefore, a build-up process has been adopted as a new multi-layered PCB manufacturing process. In this process, via-holes are used to connect each conductive layer. After the connection of the interlayers created by electro copper plating, the via-holes are filled with a conductive paste. In this study, a desmear treatment, electroless plating and electroplating were carried out to investigate the optimum processing conditions for Cu via filling on a PCB. The desmear treatment involved swelling, etching, reduction, and an acid dip. A seed layer was formed on the via surface by electroless Cu plating. For Cu via filling, the electroplating of Cu from an acid sulfate bath containing typical additives such as PEG(polyethylene glycol), chloride ions, bis-(3-sodiumsulfopropyl disulfide) (SPS), and Janus Green B(JGB) was carried out. The desmear treatment clearly removes laser drilling residue and improves the surface roughness, which is necessary to ensure good adhesion of the Cu. A homogeneous and thick Cu seed layer was deposited on the samples after the desmear treatment. The 2,2'-Dipyridyl additive significantly improves the seed layer quality. SPS, PEG, and JGB additives are necessary to ensure defect-free bottom-up super filling.
The dielectric properties and phase transformation of poled <001>-oriented Pb(Mg1/3Nb2/3)O3-x%PbTiO3(PMN-x%PT) single crystals with compositions of x=20, 30, and 35mole% are investigated for orientations both parallel andperpendicular to the [001] poling direction. An electric-field-induced monoclinic phase was observed for the initial poled PMN-30PT and PMN-35PT samples by means of high-resolution synchrotron x-ray diffraction. The monoclinic phase appears from−25oC to 100oC and from −25oC to 80oC for the PMN-30PT and PMN-35PT samples, respectively. The dielectric constant (ε)-temperature (T) characteristics above the Curie temperature were found to be described by the equation(1/ε−1/εm)1/n=(T−Tm)/C, where εm is the maximum dielectric constant and Tm is the temperature giving εm, and n and C are constants that changewith the composition. The value of n was found to be 1.82 and 1.38 for 20PT and 35PT, respectively. The results of meshscans and the temperature-dependence of the dielectric constant demonstrate that the initial monoclinic phase changes to a singledomain tetragonal phase and a to paraelectric cubic phase. In the ferroelectric tetragonal phase with a single domain state, thedielectric constant measured perpendicular to the poling direction was dramatically higher than that measured in the paralleldirection. A large dielectric constant implies easier polarization rotation away from the polar axis. This enhancement is believedto be related to dielectric softening close to the morphotropic phase boundary.
Li1+xAlxTi2-x(PO4)3(LATP) is a promising solid electrolyte for all-solid-state Li ion batteries. In this study, LATP isprepared through a sol-gel method using relatively the inexpensive reagents TiCl4. The thermal behavior, structuralcharacteristics, fractured surface morphology, ion conductivity, and activation energy of the LATP sintered bodies areinvestigated by TG-DTA, X-ray diffraction, FE-SEM, and by an impedance method. A gelation powder was calcined at 500oC.A single crystalline phase of the LiTi2(PO4)3(LTP) system was obtained at a calcination temperature above 650oC. The obtainedpowder was pelletized and sintered at 900oC and 1000oC. The LTP sintered at 900~1000oC for 6 h had a relatively low apparentdensity of 75~80%. The LATP(x=0.3) pellet sintered at 900oC for 6 h was denser than those sintered under other conditionsand showed the highest ion conductivity of 4.50×10−5S/cm at room temperature. However, the ion conductivity of LATP(x=0.3) sintered at 1000oC decreased to 1.81×10−5S/cm, leading to Li volatilization and abnormal grain growth. For LATPsintered at 900oC for 6 h, x=0.3 shows the lowest activation energy of 0.42eV in the temperature range of room temperatureto 300oC.
SnO2-mixed and Sn-doped TiO2 nanoparticles were synthesized via a hydrothermal process. SnO2-mixed TiO2 nanoparticles prepared in a neutral condition consisted of anatase TiO2 nanoparticles(diamond shape, ~25 nm) and cassiterite SnO2 nanoparticles(spherical shape, ~10 nm). On the other hand, Sn-doped TiO2 nanoparticles obtained under a high acidic condition showed a crystalline phase corresponding to rutile TiO2. As the Sn content increased, the particle shape changed from rod-like(d~40 nm, 1~200 nm) to spherical(18 nm) with a decrease in the particle size. The peak shift in the XRD results and a change of the c-axis lattice parameter with the Sn content demonstrate that the TiO2 in the rutile phase was doped with Sn. The photocatalytic activity of the SnO2-mixed TiO2 nanoparticles dramatically increased and then decreased when the SnO2 content exceeded 4%. The increased photocatalytic activity is mainly attributed to the improved charge separation of the TiO2 nanoparticles with the SnO2. In the case of Sn-doped TiO2 nanoparticles, the photocatalytic activity increased slightly with the Sn content due most likely to the larger energy bandgap caused by Sn-doping and the decrease in the particle size. The SnO2-mixed TiO2 nanoparticles generally exhibited higher photocatalytic activity than the Sn-doped TiO2 nanoparticles. This was caused by the phase difference of TiO2.
Co and Ni as catalysts in SnO2 sensors to improve the sensitivity for CH4 gas and CH3CH2CH3 gas were coated by a solution reduction method. SnO2 thick films were prepared by a screen-printing method onto Al2O3 substrates with an electrode. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a chamber. The structural properties of SnO2 with a rutile structure investigated by XRD showed a (110) dominant SnO2 peak. The particle size of the SnO2:Ni powders with Ni at 6 wt% was about 0.1 μm. The SnO2 particles were found to contain many pores according to a SEM analysis. The sensitivity of SnO2-based sensors was measured for 5 ppm of CH4 gas and CH3CH2CH3 gas at room temperature by comparing the resistance in air to that in the target gases. The results showed that the best sensitivity of SnO2:Ni and SnO2:Co sensors for CH4 gas and CH3CH2CH3 gas at room temperature was observed in SnO2:Ni sensors coated with 6 wt% Ni. The SnO2:Ni gas sensors showed good selectivity to CH4 gas. The response time and recovery time of the SnO2:Ni gas sensors for the CH4 and CH3CH2CH3 gases were 20 seconds and 9 seconds, respectively.
Magnetite nanoparticles(NPs) have been the subject of much interest by researchers owing to their potential use as magnetic carriers in drug targeting and as a tumor treatment in cases of hyperthermia. However, magnetite nanoparticles with 10 nm in diameter easily aggregate and thus create large secondary particles. To disperse magnetite nanoparticles, this study proposes the infiltration of magnetite nanoparticles into hybrid silica aerogels. The feasible dispersion of magnetite is necessary to target tumor cells and to treat hyperthermia. Magnetite NPs have been synthesized by coprecipitation, hydrothermal and thermal decomposition methods. In particular, monodisperse magnetite NPs are known to be produced by the thermal decomposition of iron oleate. In this study, we thermally decomposed iron acetylacetonate in the presence of oleic acid, oleylamine and 1,2 hexadecanediol. We also attempted to disperse magnetite NPs within a mesoporous aerogels. Methyltriethoxysilicate(MTEOS)-based hybrid silica aerogels were synthesized by a supercritical drying method. To incorporate the magnetite nanoparticles into the hybrid aerogels, we devised two methods: adding the synthesized aerogel into a magnetite precursor solution followed by nucleation and crystal growth within the pores of the aerogels, and the infiltration of magnetite nanoparticles synthesized beforehand into aerogel matrices by immersing the aerogels in a magnetite nanoparticle colloid solution. An analysis using a vibrating sample magnetometer showed that approximately 20% of the magnetite nanoparticles were well dispersed in the aerogels. The composite samples showed that heating under an inductive magnetic field to a temperature of 45˚C is possible.
Glasses were prepared with compositions of (13-x)BaO-80B2O3-7Li2O·xSm2O3, BBLSx(x=0.5, 0.4, 0.3) by melting the starting materials of boron oxide(99.9%), lithium oxide(99.9%), barium carbon oxide(99.9%), and samarium oxide(99.9%) and then quenching the melt at 1350˚C. This led to good-quality BBLSx(x=0.4, 0.3) and poor-quality BBLSx(x=0.5) glasses. The physical and structural properties of the BBLSx glasses were studied by means x-ray diffraction, scanning electron microscopy(SEM), differential scanning calorimetry(DSC), and dielectric spectroscopy. From the x-ray diffraction and SEM results, the quality of the BBLSx glasses significantly depends on the Sm2O3 concentration. The x-ray diffraction pattern showed that the crystallites in the BBLSx glasses after heat treatment at 700˚C may be LiBaB9O15. From the DSC results, the glass transition temperatures(Tg), crystallization temperatures(Tc), and the maximum temperatures of the crystallized(Tp) BBLSx glasses all changed with the Sm2O3 concentration. According to the dielectric spectroscopy results, the values of the real dielectric constant and Tan δ of the BBLSx glasses depended on the Sm2O3 concentration. The values of the real dielectric constant and Tan δ were also shown to depend on the measuring temperature, possibly due to the ion migration in the bulk of the BBLSx glasses.
In an effort to overcome the problems which arise when fabricating high-aspect-ratio TSV(through silicon via), we performed experiments involving the void-free Cu filling of a TSV(10~20 μm in diameter with an aspect ratio of 5~7) by controlling the plating DC current density and the additive SPS concentration. Initially, the copper deposit growth mode in and around the trench and the TSV was estimated by the change in the plating DC current density. According to the variation of the plating current density, the deposition rate during Cu electroplating differed at the top and the bottom of the trench. Specifically, at a current density 2.5 mA/cm2, the deposition rate in the corner of the trench was lower than that at the top and on the bottom sides. From this result, we confirmed that a plating current density 2.5 mA/cm2 is very useful for void-free Cu filling of a TSV. In order to reduce the plating time, we attempted TSV Cu filling by controlling the accelerator SPS concentration at a plating current density of 2.5 mA/cm2. A TSV with a diameter 10 μm and an aspect ratio of 7 was filled completely with Cu plating material in 90 min at a current density 2.5 mA/cm2 with an addition of SPS at 50 mg/L. Finally, we found that TSV can be filled rapidly with plated Cu without voids by controlling the SPS concentration at the optimized plating current density.
TiO2 thin films consisting of positively charged poly(diallyldimethylammonium chloride)(PDDA) and negatively charged titanium(IV) bis(ammonium lactato) dihydroxide(TALH) were successfully fabricated on glass beads by a layer-by-layer(LBL) self-assembly method. The glass beads used here showed a positive charge in an acid range and negative charge in an alkaline range. The glass beads coated with the coating sequence of(PDDA/TALH)n showed a change in the surface morphology as a function of the number of bilayers. When the number of bilayers(n) of the(PDDA/TALH) thin film was 20, Ti element was observed on the surface of the coated glass beads. The thin films coated onto the glass beads had a main peak of the (101) crystal face and were highly crystallized with XRD diffraction peaks of anatase-type TiO2 according to an XRD analysis. In addition, the TiO2 thin films showed photocatalytic properties such that they could decompose a methyl orange solution under illumination with UV light. As the number of bilayers of the(PDDA/TALH) thin film increased, the photocatalytic property of the TiO2-coated glass beads increased with the increase in the thin film thickness. The surface morphologies and optical properties of glass beads coated with TiO2 thin films with different coating numbers were measured by field emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD) and by UV-Vis spectrophotometry(UV-vis).